THATTHE TOUT UNTUK TAUS ON20170367963A1 HINDI HIT THE ( 19) United States (12 ) Patent Application Publication ( 10) Pub . No. : US 2017/ 0367963 A1 Kadir et al. (43 ) Pub . Date : Dec . 28 , 2017 (54 ) AMPHIPHILIC SUSPENSION AND Publication Classification STABILITY AGENT FOR ANTIDANDRUFF (51 ) Int. CI. HAIR CARE COMPOSITIONS A61K 8 /81 ( 2006 .01 ) A61K 8 /27 ( 2006 . 01) (71 ) Applicant: Lubrizol Advanced Materials, Inc ., A61K 8 /04 ( 2006 .01 ) Cleveland , OH (US ) A61K 8 / 49 ( 2006 .01 ) (72 ) Inventors : Murat Kadir , Brecksville , OH (US ) ; A610 5 /00 ( 2006 . 01 ) Neil Howard , Hudson , OH (US ) ; A61K 8 / 86 (2006 . 01) Shui- Jen Raymond Hsu , Westlake , OH (52 ) U . S . Cl. (US ) ; Krishnan Chari, Hudson , OH CPC ...... A61K 8 /8152 ( 2013 .01 ); A610 5 /006 (US ) ( 2013 .01 ) ; A61K 8 /86 ( 2013 .01 ) ; A61K 8 / 044 (2013 . 01 ) ; A61K 8 / 4933 ( 2013 . 01) ; A61K 8 / 27 (21 ) Appl. No. : 15 /536 ,885 (2013 .01 ) ; A61K 2800 /5422 ( 2013 .01 ) (22 ) PCT Filed : Dec . 16 , 2015 (57 ) ABSTRACT ( 86 ) PCT No. : PCT/ US2015 / 066021 A hair care composition comprising : i ) at least one cross linked nonionic amphiphilic suspending polymer ; ii ) at least $ 371 ( c ) ( 1 ) , one anionic surfactant; iii ) at least one particulate antidan ( 2 ) Date : Jun . 16 , 2017 druff agent; and iv ) water. The suspending polymer is a pH independent nonionic , amphiphilic emulsion polymer that is Related U . S . Application Data crosslinked with an amphiphilic crosslinking agent and (60 ) Provisional application No .62 / 093 ,631 , filed on Dec . effectively suspends water insoluble particulate antidandruff 18 , 2014 . agents .

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AMPHIPHILIC SUSPENSION AND ever, considering the relatively high percentage of antidan STABILITY AGENT FOR ANTIDANDRUFF druff agent incorporated into antidandruff shampoos, a sus HAIR CARE COMPOSITIONS pending agent relying only on thickening must be incorporated in such a high percentage to suspend the FIELD antidandruff agent that an unacceptably viscous product results . An increase in viscosity alone is not sufficient to [0001 ] Certain embodiments of the present technology afford permanent suspension of a dispersed phase . Stokes ' relate to antidandruff hair care compositions including a law provides that merely increasing viscosity will delay but suspension composition capable of achieving a substantial not stop separation or sedimentation of particles or droplets and unexpected reduction in the separation of insoluble suspended in a liquid . This assumes of course that the materials , such as a particulate antidandruff agent, while particles are too large to be suspended by Brownian motion . maintaining acceptable viscosities and foaming properties. Shampoos having too high a high viscosity are not accept Additionally , certain embodiments of the present technology able to consumers since they are hard to dispense , hard to concern a phase stable aqueous surfactant containing hair spread evenly on the hair and scalp , and often do not care composition comprising a pH independent amphiphilic generate adequate foam . The ideal antidandruff shampoo emulsion polymer capable of indefinitely suspending an should be thick enough to appear concentrated and rich and insoluble antidandruff agent for topical delivery to the hair, not run out of the container or hands too easily during scalp and skin . application , and be thin enough for easy dispensing from the container, ease of application to the hair and even distribu BACKGROUND tion over the scalp . [0002 ] Numerous antidandruff hair care compositions 100041 While a certain rheology modifier may thicken or such as antidandruff shampoos are commercially available enhance the viscosity of a composition in which it is or otherwise known in the art . These compositions typically included , it does not necessarily have desirable yield stress comprise water , a detersive surfactant and a particulate properties. A desirable yield stress property is critical to antidandruff agent dispersed throughout the composition . achieving certain physical and aesthetic characteristics in a Typical antidandruff agents used for this purpose include liquid medium , such as the indefinite suspension of particles , salicylic acid , sulfur, selenium sulfide or a polyvalent metal insoluble liquid droplets , or the stabilization of gas bubbles salt of pyrithione . These agents are most often insoluble or within a liquid medium . Particles dispersed in a liquid sparingly soluble in aqueous surfactant containing media , medium will remain suspended if the yield stress (yield and are present in the antidandruff composition as discrete value ) of the medium is sufficient to overcome the effect of insoluble particulate solids . For example , zinc pyrithione is gravity or buoyancy on those particles. Insoluble liquid substantially insoluble in water ( 10 -20 ppm ) . To ensure the droplets can be prevented from rising and coalescing and gas consumer of an efficacious dose of antidandruff agent during bubbles can be suspended and uniformly distributed in a each shampoo cycle , these particles should be homoge liquid medium using yield value as a formulating tool. A neously dispersed and suspended throughout the composi yield stress polymer is used generally to adjust ormodify the tion . Without a suspending agent the formulation of a phase rheological properties of aqueous compositions . Such prop stable , aqueous surfactant based antidandruff shampoo is erties include , without limitation , viscosity improvement, difficult. In order to incorporate such effective , water flow rate improvement, stability to viscosity change over insoluble antidandruff material into aqueous anionic surfac time, and the ability to suspend particles for indefinite tant- based hair shampoos , one or more suspending agents periods of time. are required to keep the antidandruff agent homogeneously [0005 ] Rheology modifiers have been used in shampoo dispersed throughout the aqueous composition and to miti products to increase viscosity at low shear rates and to gate or eliminate the settling of the insoluble antidandruff maintain flow properties at higher shear rates . In addition , it material. Failure to adequately suspend the antidandruff has been discovered that certain rheology modifiers not only material leads to eventual phase separation as the antidan• ?ang provide for a thickening effect , but also provide for effective druff material settles to the bottom of the container. Conse storage stable suspensions of insoluble and particulate mate quently , the consumer must vigorously shake the container rials in aqueous surfactant systems. Acrylic polymers have of shampoo before each use to re - disperse the antidandruff been proposed for this purpose . U . S . Pat . No. 4 ,686 , 254 active material. Manual shaking does not ensure that a discloses a suspending agent for incompatible materials in homogeneous dispersion will be attained and the deposition water based systems. Incompatible materials include anti of the active material to the hair scalp and skin during dandruff agents such as zinc pyridinethione ( zinc pyrithi - application and use may be uneven resulting in poor dan one ) . The suspending agent is a crosslinked copolymer druff control and consumer dissatisfaction . In addition , there prepared from (meth ) acrylic acid and a C1o to C30 alkyl ester may also be aesthetic and sensory negatives to the user as of (meth )acrylic acid . uneven agglomerates of insoluble particles are deposited [0006 ] U . S . Pat . No . 6 ,635 ,702 discloses a crosslinked onto the hair . acrylic emulsion polymer for use in aqueous surfactant [ 0003 ] The ideal suspending agent composition homoge containing compositions to thicken and stabilize products neously disperses the antidandruff particles throughout the containing insoluble and particulate materials including composition for an indefinite period of time without affect insoluble particulate materials such as antidandruff agents . ing the ideal viscosity , foaming , cleaning , or antidandruff The compositions are said to be stable and have an attractive properties of the shampoo . Many suspending agents operate visual appearance . on the principle of thickening the liquid to a great enough [0007 ] U . S . Pat. No. 8 , 574 , 561 concerns an antidandruff viscosity to retard the settling of particulate matter to such shampoo composition containing an antidandruff agent such an extent that the product is stable over its lifetime. How as zinc pyrithione, at least one viscosity modifying agent, at US 2017 /0367963 A1 Dec . 28 , 2017 least one acrylic based polymeric compound different from suitable neutralization of the carboxylic acid moieties on the the viscosity modifying agent, at least two surfactants cho polymer backbone with an alkaline material. Indeed , vis sen from amphoteric and zwitterionic surfactants , and cosity allows for the controlled handling and dispensing of optionally , a conditioning agent. The at least one viscosity the product during use as compared to a thinner product. In modifying agent is defined as a carbomer, and the at least personal care cleansing applications, a thick , rich shampoo one acrylic polymer different from the viscosity modifying or body cleanser is appealing to consumers from a sensory agent is defined as: 1 ) an acrylic copolymer prepared from perspective . In addition , personal care cleansing products two or more monomers consisting of (methacrylic acid or are expected to be easy to use . In other words , the shear one of its simple esters , or 2 ) a copolymer prepared from the thinning profile of the liquid composition should exhibit ester of methacrylic acid and the polyethylene glycol ether high viscosity at low shear conditions and lower viscosity at of a C12 to C22 fatty alcohol and one or more monomers of high shear conditions to aid in the application and removal (meth ) acrylic acid and one of its simple esters . A preferred of the product during use . at least one acrylic polymer different from the viscosity [0012 ] There are drawbacks associated with increasing the modifying agent is desirably crosslinked . viscosity of a product beyond its ideal viscosity . Highly [0008 ] One approach for enhancing the efficacy of anti viscous products are typically difficult to apply and rinse dandruff compositions is to maximize the deposition of zinc away, especially if the shear thinning profile of the viscosity pyrithione ( ZPT) onto the scalp by using ZPT in combina building agent is poor. High viscosities can also adversely tion with a secondary zinc salt. U . S . Pat . No. 8 ,491 , 877 affect packaging , dispensing , dissolution , and the foaming discloses an aqueous surfactant containing antidandruff and sensory properties of the product . composition including ZPT ( zinc pyridinethione ) and a zinc [ 0013 ] While a certain rheology modifier may thicken or layered material (ZLM ) obtained from a zinc salt adjuvant enhance the viscosity of a composition in which it is material. Suitable ZLM ' s include hydrozincite ( zinc carbon included , it does not necessarily have desirable yield stress ate hydroxide ) , basic zinc carbonate , aurichalcite ( zinc cop properties . A desirable yield stress property is critical to per carbonate hydroxide ) , and rosasite ( copper zinc carbon achieving certain physical and aesthetic characteristics in a ate hydroxide) with a solubility of less than 25 % . The liquid medium , such as the indefinite suspension of particles , formulator is not only challenged to provide for the effica insoluble liquid droplets , or the stabilization of gas bubbles cious suspension and dispersion of zinc pyridinethione within a liquid medium . Particles dispersed in a liquid within the formulation , equally challenging is the sparingly medium will remain suspended if the yield stress (yield soluble zinc salt adjuvant material must be dispersed evenly value ) of the medium is sufficient to overcome the effect of throughout the composition so that it does not aggregate or gravity or buoyancy on those particles . Insoluble liquid settle . droplets can be prevented from rising and coalescing and gas [ 0009 ] An embodiment of the disclosure provides a stable bubbles can be suspended and uniformly distributed in a composition for the ZLM dispersion where the ZLM zinc liquid medium using yield value as a formulating tool. A source exists in particulate form . It is revealed to be chal yield stress fluid is used generally to adjust or modify the lenging to formulate aqueous systems containing a ZLM ' s , rheological properties of aqueous compositions . Such prop due to the compound ' s unique physical and chemical prop erties include , without limitation , viscosity improvement , erties . The ZLM has a high density ( approximately 3 g / cm°) , flow rate improvement, stability to viscosity change over and needs to be evenly dispersed throughout the composi- time, and the ability to suspend particles for indefinite tion so it will not aggregate or settle . The zinc - containing periods of time. layered material also has a very -reactive surface chemistry [0014 ] Despite the well -known benefits of utilizing cross as well as the propensity to dissolve in systems with pH linked acrylic acid homopolymers and copolymers as a values below 6 . 5 . Accordingly , the pH of the composition is thickening , suspending , or rheology modifying agent , the required to be greater than 6 . 5 in order to maintain an wider use of such polymers have been limited by their effective amount of zinc ions in the formulation to increase incompatibility with formulations containing polyvalent cat the bioavailability of ZPT to exert its antidandruff activity . ions, including , as discussed above, certain materials uti [0010 ] Currently used commercial rheology modifiers are lized as antidandruff materials , e . g ., polyvalent metal salts of pH -responsive microgels , viz ., cross - linked polyacrylic acid pyridinethione , such as zinc pyrithione . polymers and alkali -swellable emulsion ( ASE ) polymers [0015 ] The degradation and storage- instability of acrylic based on ethyl acrylate and methacrylic acid . Upon neutral acid polymer thickened formulations containing sources of ization , these polymer beads swell to form a close - packed polyvalent cations has been observed in other compositions , network of swollen particles providing the shampoo with including those containing calamine and zinc oxide. His yield stress , viscosity and shear- thinning . However, these torically , formulations thickened using these polymers and pH -responsive microgels offer desired properties only containing such ingredients have been stabilized where within a limited span of pH and significant changes in possible by initial adjustment to a pH greater than 8 . 5 to 9 , properties are observed in the range of pH values close to the thereby suppressing the hydrolysis and solubilization of the PK , ( ~ 6 . 2 ) with significantly compromised yield - stress at polyvalent cations . This approach , however , is untenable for pH above the pK , in shampoo systems. Besides, these most personal formulations designed for application to anionically charged polymers are potent zinc chelating “ delicate substrates” such as hair , scalp and skin . agents that reduce ZPT therapeutic efficacy . Therefore , with [0016 ] Any antidandruff material in combination with a out a properly designed system , anti -dandruff shampoo suspending agent added to a basic detersive surfactant quality and performance can be negatively affected . chassis should provide antidandruff properties without [0011 ] The disclosed crosslinked acrylic acid copolymers detracting from the cleansing efficiency , aesthetic appeal and are viscosity building agents that increase the viscosity of therapeutic efficacy of the composition in which they are compositions in which they are dissolved or dispersed upon contained . Unfortunately , antidandruff materials , particu US 2017 /0367963 A1 Dec . 28 , 2017 larly those containing polyvalent cations, in combination composition as well as an extended range of yield stress with polymeric suspending agents that contain anionic moi properties not typically available with other polymeric thick eties often adversely affect physical properties ( e . g . foaming eners . ability , suspension stability and rheology profiles ), as well as [0022 ] In another aspect , an embodiment of the disclosed the therapeutic properties of the composition in which they technology relates to a composition and method for improv are contained . There remains the challenge of formulating ing the suspension stability of a thickened aqueous surfac compositions which can effectively suspend insoluble anti tant containing hair care composition comprising an anti dandruff materials, particularly those containing polyvalent dandruff agent, at least one surfactant and at least one cations , such as zinc pyridinethione , while at the same time silicone conditioning agent, the composition and method achieving good viscosity profiles, foam quality and suspen comprising combining a crosslinked , nonionic amphiphilic sion stability . emulsion polymer with at least one detersive surfactant selected from anionic surfactants , amphoteric surfactants , SUMMARY nonionic surfactants and combinations of two or more thereof, wherein the concentration of the amphiphilic emul [0017 ] The disclosed technology relates to a composition sion polymer is no more than 5 wt. % , and the at least one containing in an aqueous medium : surfactant is no more than 30 wt. % ( all weight percentages a ) at least one surfactant selected from an anionic , ampho are based on the total weight of the composition ) , wherein teric , and zwitter ionic surfactant; the yield stress of the composition is at least 0 . 1 Pa with a b ) at least one antidandruff agent; and shear thinning index of less than 0 . 5 at shear rates between c ) a crosslinked nonionic , amphiphilic emulsion polymer; about 0 . 1 and about 1 reciprocal seconds , and wherein the wherein the emulsion polymer is prepared from a polymer yield stress , elastic modulus and optical clarity of the izable monomer mixture comprising at least one hydrophilic composition are substantially independent of pH ranging monomer and at least one hydrophobic monomer, wherein from about 2 to about 14 . said hydrophilic monomer is selected from hydroxy ( C , - C ) [0023 ] In one aspect of the disclosed technology, the alkyl (meth )acrylates , N - vinyl amides , amino group con nonionic , amphiphilic emulsion polymer is prepared from a taining monomers , or mixtures thereof; wherein said hydro free radically polymerizable monomer composition com phobic monomer is selected from esters of (meth ) acrylic prising at least one hydrophilic monomer, at least one acid with alcohols containing 1 to 30 carbon atoms, vinyl hydrophobic monomer , and at least one crosslinking agent . esters of aliphatic carboxylic acids containing 1 to 22 carbon (0024 In an embodiment, it has been found that amphi atoms, vinyl ethers of alcohols containing 1 to 22 carbon philic crosslinking agents can be easily reacted into amphi atoms, vinyl aromatic monomers , vinyl halides , vinylidene philic polymer . Amphiphilic crosslinking agents can contain halides , associative monomers, semi- hydrophobic mono more than one reactive moiety . In some embodiments the at mers , or mixtures thereof; and wherein the amphiphilic least one reactive moiety can be an allyl group . emulsion polymer is crosslinked with at least one amphi [0025 ] In one aspect of the disclosed technology, the philic crosslinking agent containing more than one unsatu hydrophilic monomer is selected from N - vinyl amides , rated moiety . amino (C , -C3 ) alkyl (meth )acrylates , hydroxy (C1 - C5 )alkyl [ 0018 ]. It has been discovered that aqueous surfactant (meth )acrylates , amino group containing monomers , or mix containing antidandruff hair care cleansing compositions tures thereof. In one aspect , the hydrophobic monomer is possessing excellent phase stability and detersive properties selected from vinyl ester of an aliphatic carboxylic acid are obtained by incorporating at least one crosslinked , containing an acyl moiety having 2 to 22 carbon atoms, nonionic , amphiphilic emulsion polymer into the formula esters of (meth )acrylic acid with alcohols containing 1 to 30 tion to provide stable antidandruff agent containing hair care carbon atoms, vinyl ethers of alcohols containing 1 to 22 cleansing compositions. carbon atoms, vinyl aromatic monomers , vinyl halides , [0019 ] In one aspect , embodiments of the present technol vinylidene halides , associative monomers , semi- hydropho ogy relate to stable aqueous surfactant containing hair care bic monomers , or mixtures thereof. In one embodiment, the cleansing compositions comprising an antidandruff agent crosslinking monomer is selected from at least one polyun and a conditioning agent that are stabilized by at least one saturated monomer containing at least two polymerizable crosslinked , nonionic , amphiphilic emulsion polymer . unsaturated moieties . [ 0020 ] In one aspect, embodiments of the disclosed tech [0026 ] In one aspect of the disclosed technology , the nology relate to a aqueous surfactant containing hair care nonionic amphiphilic emulsion polymer is prepared from a cleansing composition comprising an antidandruff agent, a free radically polymerizable monomer composition com silicone conditioning agent and a nonionic , amphiphilic prising at least one N - vinyl amide monomer, at least one emulsion polymer which provides stable suspensions of vinyl ester of an aliphatic carboxylic acid containing an acyl pearlescent and other insoluble materials to deliver an moiety having 2 to 22 carbon atoms, and at least one aesthetic appearance and good shelf appeal. crosslinking monomer , in optional combination with at least [0021 ] In one aspect , embodiments of the disclosed tech one monomer selected from esters of (meth acrylic acid with nology relate to a aqueous surfactant containing hair care alcohols containing 1 to 30 carbon atoms, associative mono cleansing composition comprising an antidandruff agent, a mers , semi- hydrophobic monomers, or mixtures thereof. silicone conditioning agent and a crosslinked , nonionic , amphiphilic emulsion polymer which provides stable sus DESCRIPTION OF EXEMPLARY pensions of pearlescent and other insoluble materials to EMBODIMENTS deliver an aesthetic appearance and good shelf appeal over [0027 ] Exemplary embodiments in accordance with the a wide range of pH values , affording more flexibility in the disclosed technology will be described . Various modifica type of materials that can be formulated into the hair care tions , adaptations or variations of the exemplary embodi US 2017 /0367963 A1 Dec . 28 , 2017 ments described herein may become apparent to those acrylate includes acrylate as well asmethacrylate . By way of skilled in the art as such are disclosed . It will be understood further example , the term “ (methacrylamide ” includes both that all such modifications, adaptations or variations that acrylamide and methacrylamide . rely upon the teachings of the disclosed technology , and [0040 ] The term “ hair care composition ” as used herein , through which these teachings have advanced the art , are without limitation , includes shampoos, soaps , body washes , considered to be within the scope and spirit of the presently shower gels and other aqueous surfactant containing formu disclosed technology. lations normally applied to the hair , scalp and skin . [ 0028 ] The compositions, polymers and methods of the 10041 ] Here , as well as elsewhere in the specification and disclosed technology may suitably comprise , consist of, or claims, individual numerical values ( including carbon atom consist essentially of the components , elements , steps , and numerical values ) , or limits, can be combined to form process delineations described herein . The technology illus additional non - disclosed and/ or non - stated ranges . tratively disclosed herein suitably may be practiced in the [0042 ] While overlapping weight ranges for the various absence of any element which is not specifically disclosed components and ingredients that can be contained in the herein . compositions of the disclosed technology have been [0029 ] Except as otherwise noted , the articles “ a ” , “ an ” , expressed for selected embodiments and aspects of the and “ the ” mean one or more . technology , it should be readily apparent that the specific [ 0030 ] Unless otherwise stated , all percentages , parts , and amount of each component in the disclosed compositions ratios expressed herein are based upon weight of the total will be selected from its disclosed range such that the compositions of the disclosed technology. amount of each component is adjusted such that the sum of [ 0031 ] When referring to a specified monomer ( s ) that is all components in the composition will total 100 weight incorporated into a polymer of the disclosed technology, it percent. The amounts employed will vary with the purpose will be recognized that the monomer( s ) will be incorporated and character of the desired product and can be readily into the polymer as a unit ( s ) derived from the specified determined by one skilled in the art . monomerm ( s ) ( e . g ., repeating unit ). [0043 ]. The headings provided herein serve to illustrate , [0032 ] As used herein , the term “ amphiphilic polymer” but not to limit the disclosed technology in any way or means that the polymeric material has distinct hydrophilic manner. and hydrophobic portions . “ Hydrophilic ” typically means a portion that interacts intramolecularly with water and other A . Amphiphilic Emulsion Polymer polar molecules. “Hydrophobic ” typically means a portion that interacts preferentially with oils , fats or other non - polar [ 0044 ] The crosslinked , nonionic , amphiphilic polymers molecules rather than aqueous media . ( for brevity crosslinked amphiphilic polymer ) useful in the [0033 ] As used herein , the term “ hydrophilic monomer " practice of the disclosed technology are polymerized from means a monomer that is substantially water soluble . “ Sub monomer components that contain free radically polymer stantially water soluble ” refers to a material that is soluble izable unsaturation . In one embodiment, the crosslinked , in distilled ( or equivalent ) water, at 25° C ., at a concentration nonionic, amphiphilic polymers useful in the practice of the of about 3 . 5 % by weight in one aspect, and soluble at about disclosed technology are polymerized from a monomer 10 % by weight in another aspect ( calculated on a water plus composition comprising at least one nonionic , hydrophilic monomer weight basis ) . unsaturated monomer, at least one unsaturated hydrophobic [0034 ] As used herein , the term “ hydrophobic monomer ” monomer , and at least one amphiphilic polyunsaturated means a monomer that is substantially water insoluble . crosslinking monomer. In one aspect , the copolymer can be “ Substantially water insoluble ” refers to a material that is polymerized from a monomer composition comprising any not soluble in distilled ( or equivalent) water , at 25° C ., at a weight ratio of nonionic , hydrophilic unsaturated monomer concentration of about 3 % by weight in one aspect, and not to unsaturated hydrophobic monomer. soluble at about 2 . 5 % by weight in another aspect (calcu 10045 ] In one embodiment, the copolymers can be pre lated on a water plus monomer weight basis ) . pared from a monomer composition typically having a [ 00351 By " nonionic” is meant that a monomer, monomer hydrophilic monomer to hydrophobic monomer ratio of composition or a polymer polymerized from a monomer from about 5 : 95 wt. % to about 95 : 5 wt. % in one aspect , composition is devoid of ionic or ionizable moieties (“ non from about 15 : 85 wt. % to about 85 : 15 wt. % in another ionizable " ) . aspect, and from about 30 : 70 wt. % to about 70 : 30 wt. % in [0036 ] An ionizable moiety is any group that can be made a further aspect, based on the total weight of the hydrophilic ionic by neutralization with an acid or a base. and hydrophobic monomers present. The hydrophilic mono [0037 ] An ionic or an ionized moiety is any moiety that mer component can be selected from a single hydrophilic has been neutralized by an acid or a base . monomer or a mixture of hydrophilic monomers , and the [0038 ] By “ substantially nonionic ” is meant that the hydrophobic monomer component can be selected from a monomer , monomer composition or polymer polymerized single hydrophobic monomer or a mixture of hydrophobic from a monomer composition contains less than 5 wt. % in monomers . one aspect, less than 3 wt. % in another aspect, less than 1 wt. % in a further aspect, less than 0 . 5 wt. % in a still further Hydrophilic Monomer aspect , less than 0 . 1 wt. % in an additional aspect, and less 100461. The hydrophilic monomers suitable for the prepa than 0 .05 wt. % in a further aspect, of an ionizable and/ or an ration of the crosslinked , nonionic , amphiphilic emulsion ionized moiety . polymer compositions of the disclosed technology are [0039 ] The prefix “ (meth ) acryl” includes “ acryl” as well selected from but are not limited to hydroxy (C2 -C3 )alkyl as “ methacryl” . For example , the term (methacrylic (methacrylates ; open chain and cyclic N - vinylamides includes both acrylic and methacrylic , and the term (meth ) ( N - vinyllactams containing 4 to 9 atoms in the lactam ring US 2017 /0367963 A1 Dec . 28 , 2017 moiety , wherein the ring carbon atoms optionally can be [ 0051] Formula (II ) represents N - ( C2- C3) alkyl (meth ) substituted by one or more lower alkyl groups such as acrylamide or N , N -di ( C1 - C5) alkyl( meth ) acrylamide methyl, ethyl or propyl) ; amino group containing vinyl wherein R2 is hydrogen or methyl, R3 independently is monomers selected from (meth )acrylamide , N - ( C , -C3 ) selected from hydrogen , Ci to C alkyl and C? to Cg alkyl (meth ) acrylamides , N , N - di( C1 - C5) alkyl( meth ) acryl hydroxyalkyl, and R * independently is selected from is C , to amides , N - ( C , -C5 ) alkylamino ( C , -C5 ) alkyl (methacrylam C5 alkyl or C , to C5 hydroxyalkyl . ides and N , N -di ( C , -Cs ) alkylamino ( C , -C3 ) alkyl( meth ) acrylamides , wherein the alkyl moieties on the disubstituted [0052 ] Formula (III ) represents N (C2 -C3 ) alkylamino amino groups can be the same or different, and wherein the (C -C5 Jalkyl( meth )acrylamide or N ,N -di ( C1 - C5 )alkylamino alkyl moieties on the monosubstituted and disubstituted (C - C5 )alkyl ( meth )acrylamide wherein R is hydrogen or amino groups can be optionally substituted with a hydroxyl methyl, Rºis C , to C , alkylene, R ' independently is selected group ; other monomers include vinyl alcohol; vinyl imida from hydrogen or C , to C , alkyl, and R independently is zole ; and (methacrylonitrile . Mixtures of the foregoing selected from C , to C5 alkyl. monomers also can be utilized . [0053 ] Representative N -alkyl (meth )acrylamides include [ 0047 ] The hydroxy (C2 - C3 )alkyl (meth ) acrylates can be but are not limited to N -methyl ( methacrylamide , N - ethyl structurally represented by the following formula : (meth )acrylamide , N -propyl ( methacrylamide , N - isopropyl (meth ) acrylamide , N - tert- butyl (meth )acrylamide , N - (2 -hy droxyethyl) (meth )acrylamide , N -( 3 -hydroxypropyl ) ( meth ) 7 acrylamide , and mixtures thereof. - -OH [ 0054 ] Representative N , N - dialkyl( meth Jacrylamides include but are not limited to N , N -dimethyl ( meth )acrylam ide, N , N -diethyl ( meth ) acrylamide, N , N - di- 2 - hydroxyethyl ) (meth ) acrylamide, N , N - di- 3 -hydroxypropyl ) (methacryl wherein R is hydrogen or methyl and Rl is an divalent amide, N -methyl , N - ethyl( meth ) acrylamide, and mixtures alkylenemoiety containing 1 to 5 carbon atoms, wherein the thereof. alkylene moiety optionally can be substituted by one or [ 0055 ] Representative N , N - dialkylaminoalkyl( meth ) acry more methyl groups. Representative monomers include lamides include but are not limited to N , N -dimethylamino 2 - hydroxyethyl( meth ) acrylate , 3 - hydroxypropyl (meth ) acry ethyl( meth ) acrylamide, N , N -diethylaminoethylmethacryl late, 4 -hydroxybutyl (meth Jacrylate , and mixtures thereof. amide, N ,N -dimethylaminopropyl ( meth )acrylamide , and [0048 ] Representative open chain N -vinylamides include N -vinylformamide , N -methyl - N -vinylformamide , N - (hy mixtures thereof. droxymethyl) - N - vinylformamide , N - vinylacetamide , N -vi nylmethylacetamide, N - ( hydroxymethyl) - N - vinylacet Hydrophobic Monomer amide , and mixtures thereof. [0049 ] Representative cyclic N -vinylamides ( also known [0056 ] Hydrophobic monomers suitable for the prepara as N - vinyllactams) include N -vinyl - 2 -pyrrolidinone , N - 1 tion of the crosslinked , nonionic , amphiphilic emulsion methyl vinyl) pyrrolidinone , N -vinyl - 2 - piperidone , N - vinyl polymer compositions of the disclosed technology are 2 - caprolactam , N - vinyl- 5 -methyl pyrrolidinone , N - vinyl- 3 , selected from but are not limited to one or more of alkyl 3 - dimethyl pyrrolidinone , N - vinyl- 5 -ethyl pyrrolidinone esters of (methacrylic acid having an alkyl group containing and N - vinyl- 6 -methyl piperidone, and mixtures thereof . 1 to 30 carbon atoms; vinyl esters of aliphatic carboxylic Additionally , monomers containing a pendant N - vinyl acids containing 1 to 22 carbon atoms; vinyl ethers of lactam moiety can also be employed , e . g ., N - vinyl- 2 - ethyl alcohols containing 1 to 22 carbon atoms; vinyl aromatics 2 -pyrrolidone (meth )acrylate . containing 8 to 20 carbon atoms; vinyl halides ; vinylidene [0050 ] The amino group containing vinyl monomers halides; linear or branched alpha -monoolefins containing 2 include (methacrylamide , diacetone acrylamide and mono to 8 carbon atoms; an associative monomer having a hydro mers that are structurally represented by the following phobic end group containing 8 to 30 carbon atoms, and formulas: mixtures thereof.

( II) Semi- Hydrophobic Monomer [0057 ] Optionally , at least one alkoxylated semi-hydro phobic monomer can be used in the preparation of the px amphiphilic emulsion polymers of the disclosed technology. o A semi- hydrophobic monomer is similar in structure to an associative monomer , but has a substantially non -hydropho Pue bic end group selected from hydroxylor a moiety containing NH op 1 to 4 carbon atoms. 26- N R8 [ 0058 ] In one aspect , of the disclosed technology, alkyl esters of ( meth ) acrylic acid having an alkyl group containing 1 to 22 carbon atoms can be represented by the following formula : US 2017 /0367963 A1 Dec . 28 , 2017

disclosed technology ; a polyoxyalkylene mid -section por ( IV ) tion ( ii ) for imparting selective hydrophilic and /or hydro phobic properties to the product polymer, and a hydrophobic end group portion ( iii ) for providing selective hydrophobic RIO properties to the polymer. [0066 ] The portion ( i) supplying the ethylenically unsatu rated end group can be a residue derived from an a , ß ethylenically unsaturated monocarboxylic acid . Alterna wherein Rº is hydrogen or methyl and Rºis C , to C22 alkyl tively , portion ( i ) of the associative monomer can be a [ 0059 ] Representative monomers under formula (IV ) residue derived from an allyl ether or vinyl ether ; a nonionic include but are not limited to methyl (meth ) acrylate , ethyl vinyl -substituted urethane monomer , such as disclosed in (meth ) acrylate , butyl (meth ) acrylate , sec - butyl (meth ) acry U .S . Reissue Pat. No. 33 , 156 or U .S . Pat. No . 5 , 294 ,692 ; or late, iso -butyl (methacrylate , hexyl (methacrylate ), heptyl a vinyl- substituted urea reaction product, such as disclosed (meth )acrylate , octyl (meth )acrylate , 2 - ethylhexyl (meth ) in U . S . Pat. No . 5 , 011 ,978 ; the relevant disclosures of each acrylate , decyl (meth )acrylate , isodecyl (methacrylate , lau are incorporated herein by reference . ryl (meth )acrylate , tetradecyl (meth )acrylate , hexadecyl [ 0067 ] The mid - section portion ( ii ) is a polyoxyalkylene (meth )acrylate , stearyl (meth )acrylate , behenyl (methacry segment of about 2 to about 150 in one aspect, from about late, and mixtures thereof. 10 to about 120 in another aspect, and from about 15 to [0060 ] Vinyl esters of aliphatic carboxylic acids contain about 60 in a further aspect of repeating C2 -C4 alkylene ing 1 to 22 carbon atoms can be represented by the following oxide units . The mid - section portion ( ii ) includes polyoxy formula : ethylene , polyoxypropylene, and polyoxybutylene seg ments, and combinations thereof comprising from about 2 to about 150 in one aspect , from about 5 to about 120 in another aspect, from about 10 to about 60 in a further aspect , and from about 15 to about 30 in a still further aspect of ethylene , propylene and / or butylene oxide units, arranged in T R11 random or block sequences of ethylene oxide , propylene oxide and / or butylene oxide units . wherein R is a C , to C22 aliphatic group which can be an [0068 ] The hydrophobic end group portion ( iii ) of the alkyl or alkenyl. Representative monomers under formula associative monomer is a hydrocarbon moiety belonging to ( V ) include but are not limited to vinyl acetate , vinyl one of the following hydrocarbon classes : a Co -Cz linear propionate , vinyl butyrate , vinyl isobutyrate , vinyl valerate , alkyl, a C8- C30 branched alkyl, a C2 -C30 alkyl- substituted vinyl hexanoate , vinyl 2 -methylhexanoate , vinyl 2 - ethyl phenyl , aryl- substituted C2 - C30 alkyl groups, a C7- C30 satu rated or unsaturated carbocyclic alkyl group . The saturated hexanoate , vinyl iso - octanoate , vinyl nonanoate , vinyl neo or unsaturated carbocyclic moiety can be a C , -C , alkyl decanoate , vinyl decanoate , vinyl versatate , vinyl laurate , substituted or unsubstituted monocyclic or bicyclic moiety . vinyl palmitate , vinyl stearate , and mixtures thereof. In one aspect the bicyclic moiety is selected from bicyclo [0061 ] In one aspect , the vinyl ethers of alcohols contain heptyl or bicycloheptenyl. In another aspect the bicyclohep ing 1 to 22 carbon atoms can be represented by the following tenylmoiety is disubstituted with the alkyl substituent( s ) . In formula : a further aspect the bicycloheptenyl moiety is disubstituted with methyl on the same carbon atom . (VI ) [0069 ] Non - limiting examples of suitable hydrophobic end group portions ( iii ) of the associative monomers are DER13 linear or branched alkyl groups having about 8 to about 30 carbon atoms, such as capryl (C2 ) , iso -octyl (branched C ), wherein R13 is a C , to C22 alkyl. Representative monomers decyl (C10 ) , lauryl (C12 ), myristyl (C14 ) , cetyl (C16 ) , cetearyl of formula (VI ) includemethyl vinyl ether, ethyl vinyl ether , (C16 - C1s ), stearyl (C18 ), isostearyl (branched C1s) , arachidyl butyl vinyl ether , isobutyl vinyl ether, 2 - ethylhexyl vinyl (C20 ) , behenyl (C22 ) , lignoceryl (C24 ) , cerotyl (C26 ), mon ether , decyl vinyl ether, lauryl vinyl ether , stearyl vinyl ether , tanyl ( C28 ) , melissyl ( C30 ) , and the like . behenyl vinyl ether , and mixtures thereof. [0070 ] Examples of linear and branched alkyl groups 10062 ] Representative vinyl aromatic monomers include having about 8 to about 30 carbon atoms that are derived but are not limited to styrene, alpha -methylstyrene , 3 -methyl from a natural source include, without being limited thereto , styrene, 4 -methyl styrene , 4 -propyl styrene , 4 -tert -butyl alkyl groups derived from hydrogenated peanut oil, soybean styrene , 4 - n -butyl styrene, 4 - n - decyl styrene , vinyl naphtha oil and canola oil ( all predominately C18 ), hydrogenated lene , and mixtures thereof. tallow oil (C16 -C1s ) , and the like ; and hydrogenated C10 - C30 [0063 ) Representative vinyl and vinylidene halides terpenols , such as hydrogenated geraniol (branched Co) , include but are not limited to vinyl chloride and vinylidene hydrogenated farnesol ( branched Cis ), hydrogenated phytol chloride, and mixtures thereof . (branched C20 ) , and the like . [0064 ] Representative alpha - olefins include but are not [ 0071 ] Non - limiting examples of suitable C2- C30 alkyl limited to ethylene, propylene , 1 -butene , iso -butylene , substituted phenyl groups include octylphenyl, nonylphenyl, 1 - hexene , and mixtures thereof. decylphenyl, dodecylphenyl, hexadecylphenyl, octadecyl [0065 ] The associative monomer of the disclosed technol phenyl, isooctylphenyl, sec -butylphenyl , and the like. ogy has an ethylenically unsaturated end group portion ( i) [0072 ] Exemplary aryl- substituted C2- C40 alkyl groups for addition polymerization with the other monomers of the include , without limitation , styryl ( e . g . , 2 - phenylethyl) , US 2017 /0367963 A1 Dec . 28 , 2017 distyryl ( e . g . , 2 , 4 - diphenylbutyl) , tristyryl ( e . g . , 2 , 4 ,6 -triph hydroxyl group , an alkoxyl group , benzyl group phenylethyl enylhexyl) , 4 - phenylbutyl, 2 - methyl- 2 -phenylethyl , group , and a halogen group . In one aspect, Y is ethylene and tristyrylphenolyl , and the like . R16 is [ 0073 ] Suitable C2- C30 carbocyclic groups include , with out limitation , groups derived from sterols from animal sources , such as cholesterol, lanosterol, 7 - dehydrocholes CH3 terol, and the like ; from vegetable sources, such as phytos terol, stigmasterol, campesterol, and the like ; and from yeast CH3 sources, such as ergosterol, mycosterol, and the like. Other carbocyclic alkyl hydrophobic end groups useful in the disclosed technology include , without limitation , cyclooctyl, [ 0076 ] In one aspect, the hydrophobically modified asso cyclododecyl, adamantyl, decahydronaphthyl, and groups ciative monomer is an alkoxylated (meth ) acrylate having a derived from natural carbocyclic materials , such as pinene , hydrophobic group containing 8 to 30 carbon atoms repre hydrogenated retinol, camphor , isobornyl alcohol, norbornyl sented by the following Formula VB as follows: alcohol, nopol and the like . [0074 ] Useful associative monomers can be prepared by any method known in the art. See , for example , U . S . Pat. No. VIIB 4 ,421 ,902 to Chang et al. ; U . S . Pat . No . 4 ,384 ,096 to R14 Sonnabend ; U . S . Pat. No . 4 , 514, 552 to Shay et al. ; U . S . Pat . No. 4 ,600 , 761 to Ruffner et al. ; U . S . Pat. No. 4 ,616 , 074 to 20 + R15 - 07, R16 Ruffner; U . S . Pat . No. 5 ,294 ,692 to Barron et al. , U . S . Pat. No . 5 , 292 , 843 to Jenkins et al .; U . S . Pat. No . 5 ,770 ,760 to Robinson ; U . S . Pat. No . 5 , 412 , 142 to Wilkerson , III et al. ; and U . S . Pat. No. 7 ,772 , 421, to Yang et al ., the pertinent wherein R14 is hydrogen or methyl; R15 is a divalent alky disclosures of which are incorporated herein by reference . lene moiety independently selected from C2H4, 03H ., and [ 0075 ] In one aspect, exemplary associative monomers C2H , , and n represents an integer ranging from about 2 to include those represented by formulas (VII ) and (VIIA ) as about 150 in one aspect , from about 5 to about 120 in follows: another aspect , from about 10 to about 60 in a further aspect, and from about 15 to about 30 in a still further aspect, (RS _ O ) can be arranged in a random or a block configu VII ration ; R16 is a substituted or unsubstituted alkyl selected R 14 from a Cg - C30 linear alkyl, a Cg - C30 branched alkyl, an alkyl substituted and unsubstituted C -C30 carbocyclic alkyl, a 7 AFCH277 totut R15 - 07 Y - R16 C2- C30 alkyl- substituted phenyl, and an aryl - substituted C2 - C30 alkyl. VIIA [0077 ] Representative monomers under Formula V D - A + CH2 tetottR15 - 07 - Y - R16 include lauryl polyethoxylated (meth )acrylate ( LEM ), cetyl polyethoxylated (methacrylate (CEM ) , cetearyl poly wherein R14 is hydrogen or methyl; A is _ CH _ C ( O ) O - , ethoxylated (meth Jacrylate ( CSEM ) , stearyl polyethoxy - C ( O ) O - , - 0 , CH , O — . — NHC ( O )NH — , - C ( O ) lated (meth )acrylate , arachidyl polyethoxylated (meth ) acry NH?, LAr ( CE ) - NHCOÀO , Ar ( CE ) - NHC late , behenylpolyethoxylated (meth )acrylate (BEM ), cerotyl ( O ) NH — , or — CH CH NHC ( O ) — ; Ar is a divalent arylene polyethoxylated (meth )acrylate , montanyl polyethoxylated ( e .g ., phenylene ); E is H or methyl; z is 0 or 1 ; k is an integer (meth ) acrylate , melissyl polyethoxylated (methacrylate , ranging from about 0 to about 30 , and m is 0 or 1 , with the phenyl polyethoxylated (meth )acrylate , nonylphenyl poly proviso that when k is 0 , m is 0 , and when k is in the range ethoxylated (meth ) acrylate , W - tristyrylphenyl polyoxyethyl of 1 to about 30 , m is 1 ; D represents a vinyl or an allyl ene (meth )acrylate , where the polyethoxylated portion of the moiety ; (R13 - 0 ), is a polyoxyalkylene moiety , which can monomer contains about 2 to about 150 ethylene oxide units be a homopolymer , a random copolymer , or a block copo in one aspect, from about 5 to about 120 in another aspect, lymer of C2- C4 oxyalkylene units , Ris is a divalent alkylene from about 10 to about 60 in a further aspect and from about moiety selected from C2H4, C3H6, or C _Hg , and combina 15 to about 30 in a still further aspect ; octyloxy polyethyl tions thereof; and n is an integer in the range of about 2 to eneglycol ( 8 ) polypropyleneglycol ( 6 ) (meth ) acrylate , phe about 150 in one aspect, from about 10 to about 120 in noxy polyethylene glycol ( 6 ) polypropylene glycol (6 ) another aspect, and from about 15 to about 60 in a further (meth )acrylate , and nonylphenoxy polyethylene glycol aspect ; Y is - R150 — , - RISNH — , - C ( O ) - , - C ( O ) polypropylene glycol (meth )acrylate . NH , R15NHC( O )NH , C ( O ) NHC( 0 ) , or a diva [0078 ] The semi- hydrophobic monomers of the disclosed lent alkylene radical containing 1 to 5 carbon atoms, e . g . , technology are structurally similar to the associative mono methylene , ethylene , propylene, butylene , pentylene; R16 is mer described above , but have a substantially non - hydro a substituted or unsubstituted alkyl selected from a C . -C20 phobic end group portion . The semi- hydrophobic monomer linear alkyl, a C8 -C30 branched alkyl, a C2 - C30 carbocyclic , has an ethylenically unsaturated end group portion ( i ) for a C2- C30 alkyl- substituted phenyl, an araalkyl substituted addition polymerization with the other monomers of the phenyl, and an aryl- substituted C2- C30 alkyl; wherein the disclosed technology ; a polyoxyalkylene mid -section por R16 alkyl group , aryl group , phenyl group , or carbocyclic tion ( ii ) for imparting selective hydrophilic and /or hydro group optionally comprises one or more substituents phobic properties to the product polymer and a semi selected from the group consisting of a methyl group , a hydrophobic end group portion (iii ). The unsaturated end US 2017 /0367963 A1 Dec . 28 , 2017

group portion ( i) supplying the vinyl or other ethylenically [0082 ] Examples of semi- hydrophobic monomers under unsaturated end group for addition polymerization is pref formula VIIIA include polyethyleneglycol methacrylate erably derived from an a , ß - ethylenically unsaturated mono available under the product names Blemmer® PE - 90 carboxylic acid . Alternatively , the end group portion ( i) can (R14 = methyl, a = 2 , b = 0 ), PE - 200 (R14 - methyl, a = 4 .5 , b = 0 ), be derived from an allyl ether residue , a vinyl ether residue and PE -350 (R14 -methyl a = 8 , b = 0 ) ; polypropylene glycol or a residue of a nonionic urethane monomer . methacrylate available under the product names Blemmer® [ 0079 ] The polyoxyalkylene mid - section ( ii ) specifically PP - 1000 (R14 -methyl , b = 4 -6 , a = 0 ), PP -500 (R14 -methyl , comprises a polyoxyalkylene segment, which is substan a = 0 , b = 9) , PP - 800 (R14 -methyl , a = 0 , b = 13 ); polyethyl tially similar to the polyoxyalkylene portion of the associa eneglycol polypropylene glycol methacrylate available tivemonomers described above. In one aspect, the polyoxy under the product names Blemmer® 50PEP - 300 alkylene portions ( ii ) include polyoxyethylene , (R14 -methyl , a = 3 . 5 , b = 2 . 5 ), 70PEP - 350B (R14 -methyl , polyoxypropylene , and /or polyoxybutylene units compris - a = 5 , b = 2 ) ; polyethyleneglycol acrylate available under the ing from about 2 to about 150 in one aspect , from about 5 product names Blemmer® AE -90 (R14 - hydrogen , a = 2 , to about 120 in another aspect, from about 10 to about 60 , b = 0 ) , AE - 200 (R14 - hydrogen , a = 2 , b = 4 . 5 ) , AE - 400 and from about 15 to about 30 in a still further aspect in a (R14 - hydrogen , a = 10 , b = 0 ) ; polypropyleneglycol acrylate further aspect of ethylene oxide , propylene oxide , and /or available under the product names Blemmer® AP - 150 butylene oxide units, arranged in random or blocky (R14 - hydrogen , a = 0 , b = 3 ) , AP -400 ( R14 - hydrogen , a = 0 , sequences . b = 6 ), AP -550 (R14 - hydrogen , a = 0 , b = 9 ) . Blemmer® is a [0080 ] In one aspect, the semi-hydrophobic monomer can trademark of NOF Corporation , Tokyo , Japan . be represented by the following formulas: [0083 ] Examples of semi-hydrophobic monomers under formula VIIIB include methoxypolyethyleneglycol meth acrylate available under the product names Visiomer® VIII MPEG 750 MA W (R14 -methyl , a = 17 , b = 0 ) , MPEG 1005 R14 MA W (R14 =methyl , a = 22, b = 0 ), MPEG 2005 MA W (R14 - methyl, a = 45 , b = 0 ), and MPEG 5005 MA W (R14 -methyl , a = 113 , b = 0 ) from Evonik Rohm GmbH , A + CH2 th t07m + R15 – 07, R17 Darmstadt, Germany ) ; Bisomer® MPEG 350 MA IX (R14 = methyl, a = 8 , b = 0 ), and MPEG 550 MA ( R14 = methyl, D - AFCH2tk tot metR15 -07 , R17 a = 12 , b = 0 ) from GEO Specialty Chemicals , Ambler Pa. ; Blemmer® PME - 100 (R14 =methyl , a = 2 , b = 0 ), PME - 200 (R14 - methyl, a = 4 , b = 0 ) , PME - 400 (R14 - methyl, a = 9 , b = 0 ) , wherein R14 is hydrogen or methyl ; A is CH C ( 0 ) 0 — , PME - 1000 (R14 =methyl , a = 23 , b = 0 ), PME -4000 C ( O ) O _ , _ 02, CH, O — — NHC ( O) NH , C ( 0) ( R14 - methyl, a = 90 , b = 0 ) . NH?, – Ar ( CE ) - NHCUOÀO , < Ar ( CE )) - NHC ( O )NH — , or CH CH NHC ( O ) ; Ar is a divalent arylene 100841. In one aspect, the semi-hydrophobic monomer set ( e . g . , phenylene ); E is H or methyl; z is 0 or 1 ; k is an integer forth in formula IX can be represented by the following ranging from about 0 to about 30 , and m is 0 or 1 , with the formulas : proviso that when k is 0 , m is 0 , and when k is in the range CH2 = CH – O – (CH2 )d0 % (C3H60 ) - (C2H40 ) of 1 to about 30 , m is 1 ; (R15 _ O ) n is a polyoxyalkylene AH IXA moiety , which can be a homopolymer, a random copolymer, or a block copolymer of C2- C4 oxyalkylene units , R15 is a CH2= CH - CH2 -O C3H60 ) 5 — ( C2H40 )n - H IXB divalent alkylene moiety selected from C2H4, 03H . , or wherein d is an integer of 2 , 3 , or 4 ; e is an integer in the C He, and combinations thereof; and n is an integer in the range of from about 1 to about 10 in one aspect, from about range of about 2 to about 150 in one aspect, from about 5 to 2 to about 8 in another aspect, and from about 3 to about 7 about 120 in another aspect, and from about 10 to about 60 , in a further aspect; f is an integer in the range of from about and from about 15 to about 30 in a still further aspect in a 5 to about 50 in one aspect , from about 8 to about 40 in further aspect; R17 is selected from hydrogen and a linear or another aspect, and from about 10 to about 30 in a further branched C - C4 alkyl group (e . g. , methyl, ethyl, propyl, aspect ; g is an integer in the range of from 1 to about 10 in iso - propyl, butyl, iso -butyl , and tert -butyl ) ; and D represents one aspect, from about 2 to about 8 in another aspect, and a vinyl or an allyl moiety . from about 3 to about 7 in a further aspect; and h is an [0081 ] In one aspect, the semi- hydrophobic monomer integer in the range of from about 5 to about 50 in one under formula VIII can be represented by the following aspect , and from about 8 to about 40 in another aspect; e , f , formulas: g , and h can be 0 subject to the proviso that e and f cannot be 0 at the same time, and g and h cannot be 0 at the same CH2 = C (R14 ) C (0 )0 – ( C2H20 ) (C2H , 0 ) — H VIIIA time. [0085 ] Monomers under formulas IXA and IXB are com CH2 = C (R 14 ) C (0 ) 0 – ( C2H40 ) a (C3H60 ) ) CHz VIIIB mercially available under the trade names Emulsogen® wherein R14 is hydrogen or methyl , and “ a ” is an integer R109 , R208 , R307 , RAL109, RAL208 , and RAL307 sold by ranging from 0 or 2 to about 120 in one aspect, from about Clariant Corporation ; BX - AA - E5P5 sold by Bimax , Inc . ; 5 to about 45 in another aspect, and from about 10 to about and combinations thereof. EMULSOGEN7 R109 is a ran 0 .25 in a further aspect, and “ b ” is an integer ranging from domly ethoxylated /propoxylated 1, 4 -butanediol vinyl ether about 0 or 2 to about 120 in one aspect, from about 5 to about having the empirical formula CH2 = CH - O (CH2 ) 40 45 in another aspect, and from about 10 to about 25 in a (C3H60 ) 4 (C2H40 ) 10H ; Emulsogen® R208 is a randomly further aspect, subject to the proviso that “ a ” and “ b ” cannot ethoxylated /propoxylated 1 ,4 -butanediol vinyl ether having be 0 at the same time. the empirical formula CH2 = CHO ( CH2) 40 (C3H -04 US 2017 /0367963 A1 Dec . 28 , 2017

(C2H40 ) 20H ; Emulsogen® R307 is a randomly ethoxylated ) itaconic acid , maleic acid , maleic anhydride , and combina propoxylated 1 , 4 -butanediol vinyl ether having the empiri tions thereof. Other acidic monomers include styrenesulfo cal formula CH2= CH - O ( CH2) 40 ( C3H60 ) 4 (C2H40 ) 30H ; nic acid , acrylamidomethylpropanesulfonic acid ( AMPS® Emulsogen® RAL109 is a randomly ethoxylated /propoxy monomer) , vinylsulfonic acid , vinylphosphonic acid , allyl lated allyl ether having the empirical formula sulfonic acid , methallylsulfonic acid ; and salts thereof. CH2 = CHCH2O (C2H60 ) , ( C2H400H ; Emulsogen® [0091 ] Acid neutralizable monomers include olefinically RAL208 is a randomly ethoxylated /propoxylated allyl ether unsaturated monomers which contain a basic nitrogen atom having the empirical formula CH2 = CHCH2O (C3H60 ) 4 capable of forming a salt or a quaternized moiety upon the ( C2H40 ) 20H ; Emulsogen® RAL307 is a randomly ethoxy addition of an acid . For example , these monomers include lated / propoxylated allyl ether having the empirical formula vinylpyridine , vinylpiperidine , vinylimidazole, vinylmeth CH2= CHCH2O (C2H 0 ) (C2H40 )30H ; and BX -AA - E5P5 ylimidazole , dimethylaminomethyl (meth )acrylate , dimeth is a randomly ethoxylated /propoxylated allyl ether having ylaminoethyl (meth )acrylate , diethylaminomethyl (meth ) the empirical formula CH2 = CHCH2O (C2H , 0 ) ; (C2H40 ) acrylate and methacrylate , dimethylaminoneopentyl (meth ) 5H . acrylate , dimethylaminopropyl (meth )acrylate , and [0086 ] In the associative and the semi- hydrophobic mono diethylaminoethyl (methacrylate . mers of the disclosed technology, the polyoxyalkylene mid section portion contained in these monomers can be utilized Crosslinking Monomer to tailor the hydrophilicity and/ or hydrophobicity of the [ 0092 ] In one embodiment, the crosslinked , nonionic , polymers in which they are included . For example , mid amphiphilic polymers useful in the practice of the disclosed section portions rich in ethylene oxide moieties are more technology are polymerized from a monomer composition hydrophilic while mid - section portions rich in propylene comprising a first monomer comprising at least one non oxide moieties are more hydrophobic . By adjusting the ionic , hydrophilic unsaturated monomer, at least one non relative amounts of ethylene oxide to propylene oxide ionic , unsaturated hydrophobic monomer , and mixtures moieties present in these monomers the hydrophilic and thereof , and a third monomer comprising at least one poly hydrophobic properties of the polymers in which these unsaturated crosslinking monomer. The crosslinking mono monomers are included can be tailored as desired . mer( s ) is utilized to polymerize covalent crosslinks into the [0087 ] The amount of associative and /or semi-hydropho polymer backbone. The crosslinking monomer can be an bic monomer utilized in the preparation of the polymers of amphiphilic crosslinking agent or a mixture of an amphi the present disclosed technology can vary widely and philic crosslinking agent and a conventional crosslinking depends, among other things, on the final rheological and agent. aesthetic properties desired in the polymer. When utilized , 10093 ]. The crosslinking monomer can be an amphiphilic the monomer reaction mixture contains one or more mono crosslinking agent. The amphiphilic crosslinking agent is mers selected from the associative and / or semi-hydrophobic utilized to polymerize covalent crosslinks into the amphi monomers disclosed above in amounts ranging from about philic polymer backbone . In some instances , conventional 0 .01 to about 15 wt. % in one aspect, from about 0 . 1 wt . % crosslinking agents can affect the volume expansion or to about 10 wt. % in another aspect, from about 0 . 5 to about swelling of micro - gel particles in fluids containing surfac 8 wt. % in still another aspect and from about 1 , 2 or 3 to tants . For example, a high level of conventional crosslinking about 5 wt. % in a further aspect, based on the weight of the agent could provide a high yield stress but the limited total monomers . expansion of the micro - gels would result in undesirably high polymer use levels and low optical clarity . On the other Ionizable Monomer hand , a low level of conventional crosslinking agents could [ 0088 ] In one aspect of the disclosed technology , the give high optical clarity but low yield stress. It is desirable nonionic , amphiphilic emulsion polymer compositions can that polymeric micro -gels allow maximum swelling while be polymerized from a monomer composition including 0 to maintaining a desirable yield stress , and it has been found 5 wt. % of an ionizable and/ or ionized monomer, based on that the use of amphiphilic crosslinking agents in place of, the weight of the total monomers, so long as the mitigation or in conjunction with conventional crosslinking agents can of silicone deposition loss and / or the yield stress value of the provide just these benefits . In addition , it has been found that surfactant compositions in which the polymers of the dis the amphiphilic crosslinking agent can be easily reacted into closed technology are included are not deleteriously the amphiphilic polymer. Often , certain processing tech affected . niques , such as staging , can be required with conventional [0089 ] In another aspect , the amphiphilic emulsion poly crosslinking agents to achieve the proper balance of optical mer compositions of the disclosed technology can be polym clarity and yield stress . In contrast , it has been found that erized from a monomer composition comprising less than 3 amphiphilic crosslinking agents can simply be added in a wt. % in one aspect, less than 1 wt. % in a further aspect, less single stage with the monomer mixture . than 0 . 5 wt. % in a still further aspect, less than 0 . 1 wt. % [0094 Amphiphilic crosslinking agents are a subset of in an additional aspect, and less than 0 . 05 wt. % in a further compounds known in the art as reactive surfactants . Reac aspect, of an ionizable and /or an ionized moiety , based on tive surfactants are surface acting agents containing at least the weight of the total monomers . one reactive moiety so that they can covalently link to the 100901 Ionizable monomers include monomers having a surface of polymeric particles . By linking to particles , the base neutralizable moiety and monomers having an acid reactive surfactants can improve the colloidal stability of neutralizable moiety . Base neutralizable monomers include latex particles due to the surfactant' s resistance to desorbing olefinically unsaturated monocarboxylic and dicarboxylic from the particle surface . Reactive surfactants in the art acids and their salts containing 3 to 5 carbon atoms and commonly only have, or only need , one reactive moiety to anhydrides thereof. Examples include (methacrylic acid , prevent such desorption . US 2017 /0367963 A1 Dec . 28 , 2017

[0095 ] As a subset of reactive surfactants , amphiphilic [0100 ] Additionally, the amphiphilic crosslinking agent crosslinking agents as used herein are those compounds or contains multiple crosslinking moieties . Non - limiting mixtures thereof that include more than one reactive moiety . examples of crosslinking moieties can include those shown It has surprisingly been found that such amphiphilic cross - in Table A below . linking agents not only can be employed to improve stability of particles , but can be efficiently employed to prepare yield TABLE A stress fluids as described herein . [ 0096 ] The art is replete with disclosures on various types Functional Group Crosslinking Group of reactive surfactants , and one of ordinary skill in the art epoxy amine , anhydride, acid , phenolic , hydroxyl , N -methylol , aldehyde , acetoacetoxy could readily determine which include more than one reac hydroxyl isocyanate , epoxide , N -methylol , anhydride, ester tive moiety such that they can be employed herein as anhydride epoxide , amine , hydroxyl amphiphilic crosslinking agents without undue experimen cyclic carbonate Amine tation . Exemplary non - limiting amphiphilic crosslinking activated allyl amine, radical inhibitor amine aldehyde, epoxide , anhydride, isocyanate , ester , agents can be seen , for example , in U . S . Pat. No . 3 , 541 , 138 acetoacetoxy , activated allyl ( issued Nov . 17 , 1970 to Emmons et al. ) , U . S . Pat. No . silane , silicate , hydroxyl, water, acid , isocyanate , silane , silicate 6 , 262, 152 ( issued Jul. 17 , 2001 to Fryd et al. ) , U . S . Pat. No . silanol, silicone 8 , 354 , 488 ( issued Jan . 15 , 2013 to Li et al . ), WO2002 / imine aldehyde , epoxide , anhydride, isocyanate , ester , 100525 (published Dec. 19, 2002 to Syngenta ), and the like . acetoacetoxy, activated allyl [ 0097 ] The amphiphilic crosslinking agent contains a hydrophobic moiety and a hydrophilic moiety. The hydro [0101 ] Further non -limiting examples of crosslinking moi phobic moiety will provide solubility in oils , and the hydro eties can include unsaturated moieties . In an embodiment , philic moiety will provide water solubility . Hydrophobic and the amphiphilic crosslinking agent contains more than one hydrophilic moieties are well known to those skilled in the unsaturated moiety , or at least two unsaturated moieties. In art. one aspect, the amphiphilic crosslinking agent is a polyun [ 0098 ] Non - limiting examples of hydrophobic moieties of saturated compound containing at least 2 unsaturated moi the amphiphilic crosslinking agent can be derived from eties . In another aspect, the amphiphilic crosslinking agent functional groups such as alkyl, aryl, and alkyl aryl acrylates contains at least 3 unsaturated moieties . or methacrylates having 1 - 12 carbon atoms in the alkyl [0102 ] Mixtures of two or more amphiphilic crosslinking group and / or 6 - 12 carbons in the aryl group such as methyl, agents can also be utilized to crosslink the nonionic , amphi ethyl, butyl, propyl, isobutyl, hexyl, 2 - ethyl hexyl, nonyl, philic polymers . In one aspect , the mixture of amphiphilic lauryl, isobornyl, benzyl acrylates and methacrylates and the crosslinking agent contains more than one unsaturated moi like; polymerizable vinyl aromatic monomers such as sty eties , or an average of 1 . 5 or 2 unsaturated moieties . In rene , alpha methyl styrene , vinyl toluene and the like ; and another aspect, the mixture of amphiphilic crosslinking aliphatic hydrocarbon monomers such as isoprene and buta agents contains an average of 2 . 5 unsaturated moieties. In diene. Regardless of the constituent functional groups from still another aspect, the mixture of amphiphilic crosslinking which the hydrophobic moiety of the amphiphilic crosslink agents contains an average of about 3 unsaturated moieties. ing agent is derived , the hydrophobic moiety will have In a further aspect, the mixture of amphiphilic crosslinking limited solubility in water, which one of ordinary skill in the agents contains an average of about 3 . 5 unsaturated moi art would readily envisage . Examples of functional groups eties . for preparing hydrophobic moieties can include, for [0103 ] In one aspect, exemplary amphiphilic crosslinking example , alkyl phenols , stearyls, lauryls , tri - styryl phenols , agents suitable for use with the present technology can groups derived from natural oils , and the like . include , but not be limited to , compounds such as those [0099 ] Non - limiting examples of hydrophilic moieties of disclosed in US 2013 / 0047892 (published Feb . 28 , 2013 to the amphiphilic crosslinking agent can be functional groups Palmer , Jr . et al. ) , represented by the following formulas: such as ethoxylates, hydroxyls , amidos , aminos, phosphates, phosponates, sulfates, sulfonates, carboxylates and the like . Such hydrophilic moieties of the amphiphilic crosslinking agent can be derived from , for example , acid monomers such as acrylic acid , methacrylic acid , acrylamidomethyl propane sulfonic acid , itaconic acid , maleic acid and styrene YPhotz sulfonic acid and esters thereof; amine- containing mono qon mers such as 2 - dimethylaminoethylmethacrylate , 2 - dimeth ylaminoethyl acrylate , 2 -diethylaminoethyl methacrylate , and 2 -diethylaminoethyl acrylate; and monomers having oligoether moieties of the general formula : CH2= C ( R ) C ( O ) O ( C2H40 ) R1 wherein R H or methyl; R , - alkyl of 1 to 4 carbon atoms, where R = CH3, CH2CH3, C6H5, or C14H29 ; n = 1 , 2 , or 3 ; X aryl of 6 to 12 carbon atoms, or alkyl- aryl, and n = 1 to 20 , is 2 - 10 , y is 0 -200 , z is 4 - 200 , more preferably from about examples of which include ethoxyethyl methacrylate , 5 to 60 , and most preferably from about 5 to 40 ; Z can be butoxyethyl methacrylate , ethoxytriethylene methacrylate , either SO3- or PO32 - , and M * is Na+ , K + , NH4 + , or an methoxy - polyethylene glycolmethacrylate , and 2 - ethoxytri alkanolamine such as, for example, monoethanolamine , ethylene glycol methacrylate . diethanolamine , and triethanolamine ; US 2017 /0367963 A1 Dec . 28 , 2017 =

$ (IV ) QoyottyGymnotu y notre where R = CH2, CH2CH3, C6H5, or C14H29 ; n = 1 , 2 , 3 ; x is 2 - 10 , y is 0 - 200 , z is 4 - 200 , more preferably from about 5 to 60 , and most preferably from about 5 to 40 ;

( III ) R1 - 0 where n is 1 or 2 ; z is 4 to 40 in one aspect , 5 to 38 in another rthote aspect , and 10 to 20 in a further aspect ; and R4 is H , SO3- M + R2 or PO , M + , and M is selected from Na , K , and NHA.

where R is a C10 - 24 alkyl , alkaryl, alkenyl, or cycloalkyl, R2 = CH3, CH2CH3, C6H5, or C14H29 ; X is 2 -10 , y is 0 - 200 , z is 4 -200 , more preferably from about 5 to 60 , and most preferably from about 5 to 40 ; and R , is H or Z - M + Z can be either SO3 - or PO32- , and M is Na + , K +, NH4+ , or an YºMotso-o0 1 ,+5 SO3 ;- NH4NHL + alkanolamine such as , for example , monoethanolamine , diethanolamine , and triethanolamine . [ 0104 ] The foregoing amphiphilic crosslinking agents conforming to formulas ( I ) , ( 11 ) , ( III ) , (IV ) and ( V ) are disclosed in U . S . Patent Application Publication No. US 2014 /0114006 , the disclosure of which is herein incorpo rated by reference , and are commercially available under the [0108 ] In one embodiment , the crosslinking monomer can E - SperseTM RS Series trade name ( e . g ., product designations include a combination of an amphiphilic crosslinking agent RS - 1617 , RS - 1618 , RS - 1684 ) from Ethox Chemicals , LLC . and a conventional crosslinking agent. In one aspect, the [ 0105 ] In one embodiment, the amphiphilic crosslinking conventional crosslinking agent is a polyunsaturated com agent can be used in an amount ranging from about 0 .01 to pound containing at least 2 unsaturated moieties . In another aspect, the conventional crosslinking agent contains at least about 3 wt. % in one aspect, from about 0 .05 to about 0 . 1 wt. 3 unsaturated moieties . Exemplary polyunsaturated com % in another aspect , and from about 0 . 1 to about 0 .75 wt. % pounds include di( methacrylate compounds such as ethyl in a further aspect, based on the dry weight of the nonionic , ene glycol di( meth ) acrylate , polyethylene glycol di( meth ) amphiphilic polymer of the disclosed technology. acrylate , triethylene glycol di( meth ) acrylate , 1 , 3 -butylene [0106 ] In another embodiment, the amphiphilic crosslink glycol di( meth ) acrylate , 1 , 6 -butylene glycol di( meth )acry ing agent can contain an average of about 1. 5 or 2 unsatu late , 1 , 6 -hexanediol di( meth ) acrylate , neopentyl glycol rated moieties and can be used in an amount ranging from di( meth ) acrylate , 1 , 9 -nonanediol di( meth ) acrylate , 2 , 2 -bis about 0 .01 to about 3 wt. % in one aspect, from about 0 .02 ( 4 - (acryloxy -propyloxyphenyl ) propane , and 2, 2 '- bis ( 4 to about 1 wt. % in another aspect, from about 0 .05 to about (acryloxydiethoxy - phenyl) propane ; tri (meth ) acrylate com 0 .75 wt. % in a further aspect, and from about 0 .075 to about pounds such as , trimethylolpropane tri (methacrylate , trimethylolethane tri( meth ) acrylate , and tetramethylolmeth 0 . 5 wt. % in a still further aspect, and from about 0 . 1 to about ane tri (methacrylate ; tetra (methacrylate compounds such 0 . 15 wt. % in another aspect, based upon the totalweight of as ditrimethylolpropane tetra ( meth ) acrylate , tetramethylol the , nonionic , amphiphilic polymer of the disclosed tech methane tetra (methacrylate , and pentaerythritol tetra (meth ) nology acrylate ; hexamethacrylate compounds such as dipen [0107 ] In one aspect , the amphiphilic crosslinking agent is taerythritol hexa (methacrylate ; allyl compounds such as selected from compounds of formulas ( III ), (IV ) or (V ) . allyl (meth )acrylate , diallylphthalate , diallyl itaconate , dial US 2017 /0367963 A1 Dec . 28 , 2017 lyl fumarate , and diallylmaleate ; polyallyl ethers of sucrose 0 . 3 wt. % in another aspect , from about 0 .05 to about 0 .2 wt. having from 2 to 8 allyl groups per molecule , polyallyl % in a further aspect, and from about 0 . 075 to about 0 . 175 ethers of pentaerythritol such as pentaerythritol diallyl ether , wt. % in a still further aspect, and from about 0 . 1 to about pentaerythritol triallyl ether, and pentaerythritol tetraallyl 0 . 15 wt. % in another aspect , based upon the total weight of ether , and combinations thereof; polyallyl ethers of trimeth the , nonionic , amphiphilic polymer of the disclosed tech ylolpropane such as trimethylolpropane diallyl ether , trim nology ethylolpropane triallyl ether , and combinations thereof. Other suitable polyunsaturated compounds include divinyl Amphiphilic Emulsion Polymer Synthesis glycol , divinyl benzene , and methylenebisacrylamide . [ 0109 ]. In another aspect, suitable polyunsaturated mono [0116 ] The linear and crosslinked , nonionic , amphiphilic mers can be synthesized via an esterification reaction of a emulsion polymers of the disclosed technology can be made polyol made from ethylene oxide or propylene oxide or using conventional free - radical emulsion polymerization combinations thereof with unsaturated anhydride such as techniques . The polymerization processes are carried out in maleic anhydride , citraconic anhydride , itaconic anhydride , the absence of oxygen under an inert atmosphere such as or an addition reaction with unsaturated isocyanate such as nitrogen . The polymerization can be carried out in a suitable 3 - isopropenyl- a - a - dimethylbenzene isocyanate . solvent system such as water . Minor amounts of a hydro [ 0110 ] Mixtures of two or more of the foregoing polyun carbon solvent, organic solvent, as well as mixtures thereof saturated compounds can also be utilized to crosslink the can be employed . The polymerization reactions are initiated nonionic , amphiphilic polymers . In one aspect , the mixture by any means which results in the generation of a suitable of conventional unsaturated crosslinking monomer contains free - radical . Thermally derived radicals , in which the radical an average of 2 unsaturated moieties . In another aspect, the species is generated from thermal , homolytic dissociation of mixture of conventional crosslinking agents contains an peroxides, hydroperoxides , persulfates , percarbonates , per average of 2 . 5 unsaturated moieties. In still another aspect , oxyesters , hydrogen peroxide and azo compounds can be the mixture of conventional crosslinking agents contains an utilized . The initiators can be water soluble or water average of about 3 unsaturated moieties . In a further aspect, insoluble depending on the solvent system employed for the the mixture of conventional crosslinking agents contains an polymerization reaction . average of about 3 . 5 unsaturated moieties . [0117 ] The initiator compounds can be utilized in an [0111 ] In one embodiment, the conventional crosslinking amount of up to 30 wt. % in one aspect , 0 .01 to 10 wt. % in agent component can be used in an amount ranging from another aspect, and 0 . 2 to 3 wt . % in a further aspect, based about 0 .01 to about 1 wt. % in one aspect , from about 0 .05 on the total weight of the dry polymer. to about 0 .75 wt. % in another aspect, and from about 0 . 1 to [0118 ] Exemplary free radical water soluble initiators about 0 . 5 wt. % in a further aspect, based on the dry weight include , but are not limited to , inorganic persulfate com of the nonionic , amphiphilic polymer of the disclosed tech pounds, such as ammonium persulfate , potassium persulfate , nology . and sodium persulfate ; peroxides such as hydrogen perox [0112 ] In another embodiment of the disclosed technol ide , benzoyl peroxide , acetyl peroxide , and lauryl peroxide ; ogy, the conventional crosslinking agent component con organic hydroperoxides, such as cumene hydroperoxide and tains an average of about 3 unsaturated moieties and can be t -butyl hydroperoxide ; organic peracids , such as peracetic used in an amount ranging from about 0 .01 to about 0 . 3 wt. acid , and water soluble azo compounds, such as 2 , 2 ' -azobis % in one aspect, from about 0 .02 to about 0 .25 wt. % in ( tert -alkyl ) compounds having a water solubilizing substitu another aspect, from about 0 .05 to about 0 .2 wt. % in a ent on the alkyl group . Exemplary free radical oil soluble further aspect , and from about 0 .075 to about 0 . 175 wt. % in compounds include , but are not limited to 2 , 2 - azobisisobu a still further aspect, and from about 0 . 1 to about 0 . 15 wt. % tyronitrile , and the like . The peroxides and peracids can in another aspect , based upon the total weight of the , optionally be activated with reducing agents , such as sodium nonionic, amphiphilic polymer of the disclosed technology . bisulfite , sodium formaldehyde , or ascorbic acid , transition [ 0113 ] In one aspect, the conventional crosslinking agent metals , hydrazine , and the like. is selected from trimethylolpropane tri (methacrylate , trim [0119 ] In one aspect , azo polymerization catalysts include ethylolethane tri( meth Jacrylate , tetramethylolmethane tri the Vazo® free - radical polymerization initiators, available (meth ) acrylate , pentaerythritol triallylether and polyallyl from DuPont, such as Vazo® 44 ( 2 , 2 ' - azobis ( 2 - ( 4 , 5 - dihy ethers of sucrose having 3 allyl groups per molecule . droimidazolyl) propane ), Vazo® 56 ( 2, 2 '- azobis ( 2 -methyl [0114 ] In another aspect, the nonionic amphiphilic poly propionamidine ) dihydrochloride ), Vazo® 67 (2 ,2 '- azobis ( 2 mer can be crosslinked with a combination of a conventional methylbutyronitrile ) ), and Vazo® 68 ( 4 , 4 ' - azobis ( 4 crosslinking agent and an amphiphilic crosslinking agent. cyanovaleric acid )) . The conventional crosslinking agent and amphiphilic cross [0120 ] In emulsion polymerization processes, it can be linking agent can be used in a total amount ranging from advantageous to stabilize themonomer /polymer droplets or about 0 .01 to about 1 wt. % in one aspect, from about 0 . 05 particles by means of surface active auxiliaries . Typically , to about 0 .75 wt. % in another aspect, and from about 0 . 1 to these are emulsifiers or protective colloids. Emulsifiers used about 0 .5 wt. % in a further aspect , based on the dry weight can be anionic , nonionic , cationic or amphoteric . Examples of the nonionic , amphiphilic polymer of the disclosed tech of anionic emulsifiers are alkylbenzenesulfonic acids, sul nology . fonated fatty acids, sulfosuccinates, fatty alcohol sulfates, [0115 ] In another embodiment, the combination of the alkylphenol sulfates and fatty alcohol ether sulfates . conventional crosslinking agent and amphiphilic crosslink Examples of usable nonionic emulsifiers are alkylphenol ing agent can contain an average of about 2 or 3 unsaturated ethoxylates , primary alcohol ethoxylates , fatty acid ethoxy moieties and can be used in an amount ranging from about lates , alkanolamide ethoxylates , fatty amine ethoxylates , 0 .01 to about 2 wt. % in one aspect , from about 0 . 02 to about EO /PO block copolymers and alkylpolyglucosides . US 2017 /0367963 A1 Dec . 28 , 2017

Examples of cationic and amphoteric emulsifiers used are include , but are not limited to , thio - and disulfide containing quaternized amine alkoxylates , alkylbetaines , alkylamido compounds, such as C - C18 alkyl mercaptans, such as tert betaines and sulfobetaines. butyl mercaptan , n -octyl mercaptan , n - dodecyl mercaptan , [0121 ] Optionally , the use of known redox initiator sys tert- dodecyl mercaptan hexadecyl mercaptan , octadecyl tems as polymerization initiators can be employed . Such mercaptan ; mercaptoalcohols , such as 2 -mercaptoethanol , redox initiator systems include an oxidant ( intiator ) and a 2 -mercaptopropanol ; mercaptocarboxylic acids , such as reductant. Suitable oxidants include, for example , hydrogen mercaptoacetic acid and 3 -mercaptopropionic acid ; mercap peroxide , sodium peroxide , potassium peroxide , t -butyl tocarboxylic acid esters , such as butyl thioglycolate , isooctyl hydroperoxide , t - amyl hydroperoxide , cumene hydroperox thioglycolate , dodecyl thioglycolate , isooctyl 3 -mercapto ide, sodium perborate , perphosphoric acid and salts thereof, propionate , and butyl 3 -mercaptopropionate ; thioesters ; potassium permanganate , and ammonium or alkali metal C , - C18 alkyl disulfides; aryldisulfides ; polyfunctional thiols salts of peroxydisulfuric acid , typically at a level of 0 .01 % such as trimethylolpropane - tris - ( 3 -mercaptopropionate ) , to 3 . 0 % by weight, based on dry polymer weight, are used . pentaerythritol - tetra - ( 3 -mercaptopropionate ), pentaerythri Suitable reductants include , for example , alkali metal and tol- tetra- (thioglycolate ), pentaerythritol- tetra - ( thiolactate ), ammonium salts of sulfur - containing acids, such as sodium dipentaerythritol- hexa -( thioglycolate ), and the like; phos sulfite , bisulfite , thiosulfate , hydrosulfite , sulfide , hydrosul phites and hypophosphites; C , -C4 aldehydes, such as form fide or dithionite , formadinesulfinic acid , hydroxymethane aldehyde , acetaldehyde , propionaldehyde ; haloalkyl com sulfonic acid , acetone bisulfite , amines such as etha pounds , such as carbon tetrachloride , nolamine , glycolic acid , glyoxylic acid hydrate , ascorbic bromotrichloromethane , and the like ; hydroxylammonium acid , isoascorbic acid , lactic acid , glyceric acid , malic acid , salts such as hydroxylammonium sulfate ; formic acid ; 2 - hydroxy - 2 - sulfinatoacetic acid , tartaric acid and salts of sodium bisulfite ; isopropanol; and catalytic chain transfer the preceding acids typically at a level of 0 .01 % to 3 .0 % by agents such as , for example , cobalt complexes ( e . g . , cobalt weight , based on dry polymer weight, is used . In one aspect , ( II) chelates ) . combinations of peroxodisulfates with alkali metal or [0126 The chain transfer agents are generally used in ammonium bisulfites can be used , for example, ammonium amounts ranging from 0 . 1 to 10 wt. % , based on the total peroxodisulfate and ammonium bisulfite . In another aspect , weight of the monomers present in the polymerization combinations of hydrogen peroxide containing compounds medium . ( t -butyl hydroperoxide ) as the oxidant with ascorbic or erythorbic acid as the reductant can be utilized . The ratio of Emulsion Process peroxide - containing compound to reductant is within the [0127 ] In one exemplary aspect of the disclosed technol range from 30 : 1 to 0 . 05 : 1. ogy , the crosslinked , nonionic , amphiphilic emulsion poly [0122 ] In emulsion polymerization processes it can be mer is polymerized via an emulsion process . The emulsion advantageous to stabilize the monomer/ polymer droplets or process can be conducted in a single reactor or in multiple particles by means of surface active auxiliaries. Typically , reactors as is well -known in the art. The monomers can be these are emulsifiers or protective colloids . Emulsifiers used added as a batch mixture or each monomer can be metered can be anionic , nonionic , cationic or amphoteric . Examples into the reactor in a staged process . A typical mixture in of anionic emulsifiers are alkylbenzenesulfonic acids, sul emulsion polymerization comprises water, monomer( s ), an fonated fatty acids, sulfosuccinates , fatty alcohol sulfates , initiator (usually water - soluble ) and an emulsifier . The alkylphenol sulfates and fatty alcohol ether sulfates . monomers may be emulsion polymerized in a single -stage , Examples of usable nonionic emulsifiers are alkylphenol two - stage or multi- stage polymerization process according ethoxylates , primary alcohol ethoxylates, fatty acid ethoxy to well - known methods in the emulsion polymerization art. lates , alkanolamide ethoxylates, fatty amine ethoxylates , In a two - stage polymerization process , the first stage mono EO /PO block copolymers and alkylpolyglucosides . mers are added and polymerized first in the aqueous Examples of cationic and amphoteric emulsifiers used are medium , followed by addition and polymerization of the quaternized amine alkoxylates, alkylbetaines, alkylamido second stage monomers . The aqueous medium optionally betaines and sulfobetaines . can contain an organic solvent. If utilized the organic solvent [0123 ] Examples of typical protective colloids are cellu is less than about 5 wt. % of the aqueous medium . Suitable lose derivatives, polyethylene glycol, polypropylene glycol, examples of water- miscible organic solvents include , with copolymers of ethylene glycol and propylene glycol, poly out limitation , esters, alkylene glycol ethers, alkylene glycol vinyl acetate , poly (vinyl alcohol) , partially hydrolyzed poly ether esters , lower molecular weight aliphatic alcohols , and ( vinyl alcohol ), polyvinyl ether, starch and starch deriva the like . tives , dextran , polyvinylpyrrolidone , polyvinylpyridine , 0128 ] To facilitate emulsification of the monomer mix polyethyleneimine , polyvinylimidazole, polyvinylsuccinim ture , the emulsion polymerization is carried out in the ide , polyvinyl- 2 -methylsuccinimide , polyvinyl- 1 , 3 - ox presence of at least one surfactant. In one embodiment, the azolid - 2 - one , polyvinyl - 2 -methylimidazoline and maleic emulsion polymerization is carried out in the presence of acid or anhydride copolymers . The emulsifiers or protective surfactant ( active weight basis ) ranging in the amount of colloids are customarily used in concentrations from 0 . 05 to about 0 . 2 % to about 5 % by weight in one aspect , from about 20 wt. % , based on the weight of the total monomers . 0 . 5 % to about 3 % in another aspect, and from about 1 % to [ 0124 ] The polymerization reaction can be carried out at about 2 % by weight in a further aspect, based on a total temperatures ranging from 20 to 200° C . in one aspect, from monomer weight basis . The emulsion polymerization reac 50 to 150° C . in another aspect, and from 60 to 100° C . in tion mixture also includes one or more free radical initiators a further aspect which are present in an amount ranging from about 0 .01 % 0125 ] The polymerization can be carried out the presence to about 3 % by weight based on total monomer weight. The of chain transfer agents . Suitable chain transfer agents polymerization can be performed in an aqueous or aqueous US 2017 /0367963 A1 Dec . 28 , 2017 14 alcohol medium . Surfactants for facilitating the emulsion initiator is injected into the so formed aqueous surfactant polymerization include anionic , nonionic , amphoteric , and solution in the second reactor, and the monomer emulsion cationic surfactants , as well as mixtures thereof. Most com from the first reactor is gradually metered into the second monly , anionic and nonionic surfactants can be utilized as reactor over a period typically ranging from about one half well as mixtures thereof. to about four hours. The reaction temperature is controlled [0129 ] Suitable anionic surfactants for facilitating emul in the range of about 45 to about 95° C . After completion of sion polymerizations are well known in the art and include, the monomer addition , an additional quantity of free radical but are not limited to (C6 - C18 ) alkyl sulfates, (CG -C18 ) alkyl initiator can optionally be added to the second reactor, and ether sulfates ( e . g ., sodium lauryl sulfate and sodium laureth the resulting reaction mixture is typically held at a tempera sulfate ) , amino and alkali metal salts of dodecylbenzenesul ture of about 45 to 95° C . for a time period sufficient to fonic acid , such as sodium dodecyl benzene sulfonate and complete the polymerization reaction to obtain the polymer dimethylethanolamine dodecylbenzenesulfonate , sodium emulsion . (C6 - C16) alkyl phenoxy benzene sulfonate , disodium (Co [0134 ] In one aspect, the crosslinked , nonionic , amphiphi Co) alkyl phenoxy benzene sulfonate , disodium ( C . -C16 ) lic polymers of the disclosed technology are selected from di- alkyl phenoxy benzene sulfonate , disodium laureth -3 an emulsion polymer polymerized from a monomer mixture sulfosuccinate, sodium dioctyl sulfosuccinate , sodium di comprising from about 20 to about 60 wt. % of at least one sec -butyl naphthalene sulfonate , disodium dodecyl diphenyl CZ -C4 hydroxyalkyl (meth ) acrylate ( e . g ., hydroxyethyl ether sulfonate, disodium n - octadecyl sulfosuccinate , phos methacrylate ); from about 10 to about 70 wt. % of at least phate esters of branched alcohol ethoxylates, and the like . one C , -Co , 2 alkyl (meth )acrylate in one aspect or from [0130 ] Nonionic surfactants suitable for facilitating emul about 10 to about 70 wt. % of at least one C -Cos alkyl sion polymerizations are well known in the polymer art , and (meth )acrylate in another aspect; from about 0 , 1 , 5 or 15 to include, without limitation , linear or branched C8 -C30 fatty about 40 wt. % of at least one vinyl ester of a C , -C10 alcohol ethoxylates, such as capryl alcohol ethoxylate , lauryl carboxylic acid , from about 0 , 1 or 15 to about 30 wt. % of alcohol ethoxylate , myristyl alcohol ethoxylate , cetyl alco a vinyl lactam ( e . g . , vinyl pyrrolidone ); from about 0 , 0 . 1 , 1 , hol ethoxylate , stearyl alcohol ethoxylate , cetearyl alcohol 5 , or 7 to about 15 wt. % of at least one associative and / or ethoxylate , sterol ethoxylate , oleyl alcohol ethoxylate , and , a semi- hydrophobic monomer (wherein all monomer weight behenyl alcohol ethoxylate ; alkylphenol alkoxylates, such as percentages are based on the weight of the total monomers ) ; octylphenol ethoxylates; and polyoxyethylene polyoxypro and from about 0 .01 to about 5 wt . % in one aspect, from pylene block copolymers , and the like . Additional fatty about 0 . 1 to about 3 in another aspect, and from about 0 . 5 alcohol ethoxylates suitable as non - ionic surfactants are to about 1 wt. % in a further aspect of at least one crosslinker described below . Other useful nonionic surfactants include (based on the dry weight of the polymer ), wherein the at 08 -022 fatty acid esters of polyoxyethylene glycol, ethoxy least one crosslinker is selected from an amphiphilic cross lated mono - and diglycerides, sorbitan esters and ethoxy linking agent or a combination of an amphiphilic crosslink lated sorbitan esters, 08 -022 fatty acid glycol esters , block ing agent and a conventional crosslinking agent as defined copolymers of ethylene oxide and propylene oxide , and herein . combinations thereof. The number of ethylene oxide units in [0135 ]. In another aspect, the crosslinked , nonionic , each of the foregoing ethoxylates can range from 2 and amphiphilic polymers of the disclosed technology are above in one aspect , and from 2 to about 150 in another selected from an emulsion polymer polymerized from a aspect . monomermixture comprising from about 20 to about 50 wt. [0131 ] Optionally , other emulsion polymerization addi % at least one C , - C4 hydroxyalkyl (meth )acrylate (e . g . , tives and processing aids which are well known in the hydroxyethyl methacrylate ) ; from about 10 to about 30 wt. emulsion polymerization art , such as auxiliary emulsifiers , % ethyl acrylate ; from about 10 to about 35 wt. % butyl protective colloids, solvents , buffering agents , chelating acrylate ; from about 0 or 15 to about 25 wt. % of a vinyl agents , inorganic electrolytes , polymeric stabilizers, bio ester of a C , - C , carboxylic acid selected from vinyl formate , cides , and pH adjusting agents can be included in the vinyl acetate , vinyl propionate, vinyl butyrate , vinyl isobu polymerization system . tyrate, and vinyl valerate ; from about 0 , 1 or 15 to about 30 [0132 ] In one embodiment of the disclosed technology , the wt. % of vinyl pyrrolidone ; and from about 0 , 0 . 1 , 1 , 5 or 7 protective colloid or auxiliary emulsifier is selected from to about 15 wt . % of at least one associative monomer and /or poly (vinyl alcohol) that has a degree of hydrolysis ranging semi- hydrophobic monomer (wherein all monomer weight from about 80 to 95 % in one aspect , and from about 85 to percentages are based on the weight of the totalmonomers ) ; 90 % in another aspect. and from about 0 .01 to about 5 wt. % in one aspect , from [ 0133] In a typical two stage emulsion polymerization , a about 0 . 1 to about 3 in another aspect , and from about 0 . 5 mixture of the monomers is added to a first reactor under to about 1 in a further aspect of at least one crosslinker inert atmosphere to a solution of emulsifying surfactant (based on the dry weight of the polymer) , wherein the at ( e . g . , anionic surfactant) in water . Optional processing aids least one crosslinker is selected from an amphiphilic cross can be added as desired ( e . g ., protective colloids, auxiliary linking agent or a combination of an amphiphilic crosslink emulsifier ( s ) ) . The contents of the reactor are agitated to ing agent and a conventional crosslinking agent as defined prepare a monomer emulsion . To a second reactor equipped herein . with an agitator, an inert gas inlet , and feed pumps are added 10136 ] In another embodiment, the crosslinked , nonionic , under inert atmosphere a desired amount of water and amphiphilic polymers of the disclosed technology are additional anionic surfactant and optional processing aids. selected from an emulsion polymer polymerized from a The contents of the second reactor are heated with mixing monomer mixture comprising from about 20 to about 50 wt. agitation . After the contents of the second reactor reaches a % of hydroxyethyl methacrylate ; from about 10 to about 30 temperature in the range of about 55 to 98° C ., a free radical wt. % ethyl acrylate; from about 10 to about 30 wt. % butyl US 2017 /0367963 A1 Dec . 28 , 2017 15 acrylate ; from about 0 , 1 , or 15 to about 25 wt. % of vinyl [0140 ] In one aspect , the crosslinked , nonionic , amphiphi pyrrolidone ; from about 0 or 15 to about 25 wt. % of vinyl lic polymers of the disclosed technology are selected from acetate ; from about 0 , 0 . 1 , 1 , 5 or 7 to about 10 wt. % of at an emulsion polymer polymerized from a monomer mixture least one associative and /or semi-hydrophobic monomer comprising from about 20 to 40 wt. % of hydroxyethyl (wherein all monomer weight percentages are based on the methacrylate , from about 10 to about 30 wt. % ethyl weight of the totalmonomers ); and from about 0 .01 to about acrylate , from about 10 to about 30 wt. % butyl acrylate , 5 wt. % in one aspect, from about 0 . 1 to about 3 wt. % in from about 15 to about 25 wt. % of vinyl pyrrolidone , and another aspect, and from about 0 . 5 to about 1 wt. % in a from about 1 to about 5 wt. % of at least one associative further aspect of at least one crosslinker (based on the dry and / or semi-hydrophobic monomer (wherein all monomer weight of the polymer ) , wherein the at least one crosslinker weight percentages are based on the weight of the total is selected from an amphiphilic crosslinking agent or a monomers ) , and from about 0 . 01 to about 5 wt. % in one combination of an amphiphilic crosslinking agent and a aspect , from about 0 . 1 to about 3 wt. % in another aspect , conventional crosslinking agent as defined herein . and from about 0 .5 to about 1 wt. % in a further aspect of [0137 ] In another embodiment, the crosslinked , nonionic , at least one crosslinker (based on the dry weight of the amphiphilic polymers of the disclosed technology are polymer ) , wherein the at least one crosslinker is selected selected from an emulsion polymer polymerized from a from an amphiphilic crosslinking agent or a combination of monomer mixture comprising from about 20 to 50 wt. % of an amphiphilic crosslinking agent and a conventional cross hydroxyethylmethacrylate ; from about 10 to about 40 wt. % linking agent as defined herein . ethyl acrylate ; from about 10 to about 20 wt. % butyl (0141 ] In another aspect, the at least one nonionic , amphi acrylate ; from about 0 . 1 to about 10 wt. % of at least one philic emulsion polymer utilized in formulating the hair care associative and / or semi-hydrophobic monomer (wherein all compositions of the disclosed technology is crosslinked . The monomer weight percentages are based on the weight of the crosslinked nonionic , amphiphilic emulsion polymers of the total monomers ) ; and from about 0 .01 to about 5 wt. % in technology are random copolymers and have weight average one aspect, from about 0 .1 to about 3 wt. % in another molecular weights ranging from above about 500 ,000 to at aspect , and from about 0 . 5 to about 1 wt. % in a further least about a billion Daltons or more in one aspect , and from aspect of at least one crosslinker (based on the dry weight of about 600 , 000 to about 4 . 5 billion Daltons in another aspect , the polymer ), wherein the at least one crosslinker is selected and from about 1, 000 , 000 to about 3 ,000 , 000 Daltons in a from an amphiphilic crosslinking agent or a combination of further aspect, and from about 1, 500 ,000 to about 2 ,000 ,000 an amphiphilic crosslinking agent and a conventional cross Daltons in a still further aspect ( see TDS - 222 , Oct. 15 , 2007, linking agent as defined herein . Lubrizol Advanced Materials , Inc . , which is herein incor [0138 ] In one aspect , the crosslinked , nonionic , amphiphi porated by reference ). lic polymers of the disclosed technology are selected from an emulsion polymer polymerized from a monomer mixture B . Antidandruff Agents comprising from about 20 to 50 wt. % of hydroxyethyl [ 0142 ] The antidandruff agents of the present technology methacrylate ; from about 10 to about 30 wt. % ethyl are any particulate compound capable of relieving the symp acrylate ; from about 10 to about 30 wt. % butyl acrylate ; toms of dandruff and that are substantive to the hair , scalp from about 1 to about 10 wt. % of at least one associative and skin to afford residual antidandruff properties between and / or semi- hydrophobic monomer (wherein all monomer shampoos. Among the many particulate compounds exhib weight percentages are based on the weight of the total iting antidandruff properties that are useful herein are sali monomers ) ; and from about 0 .01 to about 5 wt. % in one cylic acid , elemental sulfur, selenium sulfides , azole com aspect, from about 0 . 1 to about 3 wt. % in another aspect, pounds , 2 - pyridone derivatives based on 1 -hydroxy - 2 and from about 0 .5 to about 1 wt. % in a further aspect of pyridone , and polyvalent metal salts of pyrithione . at least one crosslinker (based on the dry weight of the 0143 ] Sulfur is a particulate antidandruff agent that is polymer ), wherein the at least one crosslinker is selected effective in the compositions of the disclosed technology . from an amphiphilic crosslinking agent or a combination of Sulfur can be utilized in an amount ranging from about 1 wt. an amphiphilic crosslinking agent and a conventional cross % to about 5 wt. % in one aspect, and from about 2 wt. % linking agent as defined herein . to about 4 wt. % in another aspect, based on the weight of [0139 ] In one aspect, the crosslinked , nonionic , amphiphi the total composition . lic polymers of the disclosed technology are selected from [0144 ] Selenium sulfide is a particulate anti -dandruff an emulsion polymer polymerized from a monomer mixture agent suitable for use in the antidandruff compositions of the comprising from about 20 to 35 wt. % of hydroxyethyl present technology and is selected from compounds of the methacrylate , from about 10 to about 30 wt. % ethyl formula Sex S , where x is a number ranging from 1 to 7 . acrylate , from about 10 to about 30 wt. % butyl acrylate , Effective concentrations of selenium sulfide can range from from about 15 to about 25 wt. % of vinyl pyrrolidone , from about 0 . 1 % to about 4 wt. % in one aspect , from about 0 . 3 % about 15 to about 25 wt. % of vinyl acetate (wherein all to about 2 . 5 wt. % in another aspect, and from about 0 . 5 % monomer weight percentages are based on the weight of the to about 1. 5 wt. % in still another aspect , based on the weight total monomers ), and from about 0 .01 to about 5 wt. % in of the composition . one aspect , from about 0 . 1 to about 3 wt. % in another [0145 ] The azole antidandruff agents include imidazoles aspect , and from about 0 . 5 to about 1 wt. % in a further such as benzimidazole , benzothiazole , bifonazole , butocon aspect of at least one crosslinker (based on the dry weight of azole nitrate , climbazole , clotrimazole , croconazole, eber the polymer ) , wherein the at least one crosslinker is selected conazole , econazole , elubiol, fenticonazole , fluconazole , from an amphiphilic crosslinking agent or a combination of flutimazole , isoconazole , ketoconazole , lanoconazole , met an amphiphilic crosslinking agent and a conventional cross ronidazole , miconazole, neticonazole , omoconazole, oxi linking agent as defined herein . conazole nitrate , sertaconazole , sulconazole nitrate , tiocon US 2017 /0367963 A1 Dec . 28 , 2017 16

azole , thiazole , and triazoles such as terconazole and [0149 ] In one aspect the ZPT antidandruff agent has an itraconazole, and combinations thereof. When present in the average particle size of up to about 20 um in one aspect, up composition , the azole antidandruff agent can be included in to about 5 um in another aspect , up to about 2 . 5 um in still an amount from about 0 .01 % to about 5 wt. % in one aspect, another aspect, and up to about 1 um in a further aspect . In from about 0 . 1 % to about 3 wt. % in another aspect, and an additional embodiment the average particle size can from about 0 . 3 % to about 2 wt. % in still another aspect, range from about 0 . 1 um to about 1 um in one aspect, and based on the weight of the composition . from about 0 .25 um to about 0 .75 um in another aspect . The [0146 ] Exemplary antidandruff agents that are based on average particle size can be measured by light scattering 1 -hydroxy - 2 - pyridone are 1 -hydroxy - 4 -methyl - 2 -pyridone , techniques well- known in the art for determining average 1 -hydroxy -6 -methylpyridone , 1 - hydroxy - 4 ,6 - dimethyl- 2 particle size for particulate materials . One such method pyridone , 1- hydroxy - 4 -methyl - 6 - (2 ,4 ,4 - trimethylpentyl) - 2 involves measuring particle size by means of a laser light pyridone, 1 - hydroxy - 4 -methyl - 6 - cyclohexyl- 2 -pyridone , scattering technique using a Horiba model LA 910 laser 1 - hydroxy - 4 -methyl - 6 - (methyl - cyclohexyl ) 2 -pyridone , scattering particle size distribution analyzer (Horiba Instru 1 - hydroxy - 4 -methyl - 6 - ( 2 -bicyclo [ 2 , 2 , 1 ]heptyl ) - 2 -pyridone , ments , Inc. , Irvine, Calif. ) . 1 -hydroxy - 4 -methyl - 6 (4 -methylphenyl ) - 2 -pyridone , 1 -hy [0150 ] Pyridinethione anti- microbial and anti- dandruff droxy - 4 -methyl -6 [ 1 - [ 4 - nitrophenoxy ] -butyl ] - 2 -pyridone , agents are described , for example , in U . S . Pat. No . 2, 809, 1 - hydroxy - 4 -methyl - 6 - ( 4 - cyanophenoxymethyl- 2 - pyri 971 ; U . S . Pat. No. 3 , 236 , 733 ; U . S . Pat . No . 3 , 753 , 196 ; U . S . done ), 1 -hydroxy - 4 -methyl - 6 - (phenylsulfonylmethyl ) - 2 Pat . No. 3 ,761 ,418 ; U . S . Pat. No. 4 , 345 ,080 ; U . S . Pat . No . pyridone , 1- hydroxy -4 -methyl - 6 - ( 4 -bromobenzyl ) - 2 -pyri 4 , 323 ,683 ; U . S . Pat . No. 4 ,379 ,753 ; and U . S . Pat . No . done and salts thereof. In one embodiment , the 4 ,470 ,982 . Zinc pyrithione can be made by reacting 1 -hy monoethanolamine salt of 1 - hydroxy - 4 -methyl - 6 - ( 2 , 4 , 4 droxy - 2 -pyridinethione ( i. e ., pyrithione acid ) or a soluble trimethylpenthyl) -2 -pyridone , monoethanolamine salt avail salt thereof with a zinc salt ( e . g . zinc sulfate ) to form a zinc able from Clariant under the trade name Octopirox® is a pyrithione precipitate , as illustrated in U . S . Pat. No. 2 ,809 . suitable antidandruff agent. 971. Zinc pyrithione is commercially available from Arch [0147 ] The polyvalent metal salts of pyrithione include Chemicals , Inc . (Lonza Group Ltd . ), under the trade name those formed from the polyvalent metals magnesium , Zinc OrmadineTM barium , bismuth , strontium , copper , zinc , cadmium , zirco 10151] In one embodiment the amount of polyvalent metal nium and mixtures thereof. The polyvalent metal salts of salt of pyrithione ( e . g . , ZPT ) suitable for use in the compo pyrithione can be represented by Formula X as follows : sitions of the present technology range from about 0 .01 wt. % to about 5 wt. % in one aspect, and from about 0 . 1 wt. % to about 2 wt. % in another aspect , based on the weight of the composition . [0152 ] In one embodiment of the present technology, the polyvalent metal salt of pyrithione can be used in combi M ' s nation with a secondary particulate zinc salt as disclosed in U . S . Pat. Application Pub . No . 2004 /0213751 and U . S . Pat . . No . 8 ,491 , 877 , the pertinent disclosures of which are incor porated herein by reference . It is disclosed that zinc con taining layered materials (ZLM ) are useful secondary salts in which M is a polyvalent metal ion selected from magne that augment the antimicrobial efficacy of polyvalent metal sium , barium , bismuth , strontium , copper , zinc , cadmium salts of pyrithione, particularly ZPT . and zirconium , and n corresponds to the valency of M . Any [0153 ] Exemplary ZLM 's include , but are not limited to , physical form of polyvalent metal pyrithione salts can be hydrozincite ( zinc carbonate hydroxide ) , basic zinc carbon used , including platelet and needle configurations. ate , aurichalcite ( zinc copper carbonate hydroxide ) , rosasite [ 0148 ] In one embodiment the polyvalent metal salt of ( copper zinc carbonate hydroxide ) and many related miner pyrithione is selected from the zinc salt of 1 -hydroxy - 2 als that are zinc -containing . Natural ZLM ' s can also occur pyridinethione , i. e . , the zinc complex of 2 - pyridinethiol - 1 wherein anionic layer species such as clay - type minerals oxide (known as “ zinc pyrithione” or “ ZPT" ) represented by ( e . g ., phyllosilicates ) contain ion -exchanged zinc gallery Formula XA as follows: ions . [0154 ] In one embodiment, basic zinc carbonate is used in XA combination with ZPT . Basic zinc carbonate , which also is referred to commercially as “ zinc carbonate ” or “ zinc car bonate basic ” or “ zinc hydroxy carbonate ” , is a synthetic version consisting of materials similar to naturally occurring hydrozincite . The idealized stoichiometry is represented as Zn (OH ) . (CO3 ) 2 , but the actual stoichiometric ratios can N vary slightly and other impurities may be incorporated in the crystal lattice . Commercially available sources of basic Zinc Carbonate include Zinc Carbonate Basic (Cater Chemicals : Bensenville , 111 ., USA ), Zinc Carbonate Basic (Sigma - Al drich : St. Louis , Mo ., USA ) , Zinc Carbonate ( Shepherd Chemicals : Norwood , Ohio , USA ), Zinc Carbonate (CPS Union Corp . : New York , N . Y . , USA ) , Zinc Carbonate ( El US 2017 /0367963 A1 Dec . 28 , 2017 ementis Pigments : Durham , UK ), and Zinc Carbonate AC anionic surfactant, and an optional surfactant selected from (Bruggemann Chemical: Newtown Square, Pa. , USA ) . amphoteric or zwitterionic surfactants , nonionic surfactants , [ 0155 ] In aspect of the present technology, the ZLM ( e . g ., and mixtures thereof. basic zinc carbonate ) can have a particle size distribution [0162 ] Non - limiting examples of anionic surfactants are wherein 90 % of the particles are less than about 50 um . In disclosed in McCutcheon 's Detergents and Emulsifiers , another aspect , the ZLM can have a particle size distribution North American Edition , 1998 , published by Allured Pub wherein 90 % of the particles are less than about 30 um . In lishing Corporation ; and McCutcheon ' s , Functional Mate yet a further aspect , the ZLM can have a particle size rials, North American Edition ( 1992 ) ; both of which are distribution wherein 90 % of the particles are less than about incorporated by reference herein in their entirety . The 20 um . anionic surfactant can be any of the anionic surfactants [0156 ] In another aspect of the present technology , the known or previously used in the art of aqueous surfactant ZLM ( e . g . , basic zinc carbonate ) can have a surface area of compositions, including synthetic surfactants ( syndets ) and greater than about 10 m2/ gm . In a further aspect , the ZLM fatty acid soaps. can have a surface area of greater than about 20 m?lgm . In yet a further aspect of the ZLM can have a surface area of 10163 ] Suitable anionic syndet surfactants include but are greater than about 30 m´/ gm . not limited to alkyl sulfates , alkyl ether sulfates alkyl [ 0157 ] In embodiments utilizing a ZLM and a polyvalent sulfonates , alkylaryl sulfonates, alkenyl and hydroxyalkyl metal salt of pyrithione ( e . g . ZPT ) , the ratio of ZLM to alpha - olefin - sulfonates, and mixtures thereof, alkylamide polyvalent metal salt of pyrithione is from about 5 : 100 to sulfonates , alkarylpolyether sulphates , alkylamidoether sul about 10 : 1 in one aspect, from about 2 : 10 to about 5 : 1 in phates , alkyl and alkenyl monoglyceryl ether sulfates, alkyl another aspect , and from about 1 : 2 to about 3 : 1 in still and alkenyl monoglyceride sulfates, alkyl and alkenyl another aspect (all ratios based on a wt. / wt. basis ) . monoglyceride sulfonates, alkyl and alkenyl succinates , (0158 ] In one embodiment of the present technology , the alkyl and alkenyl sulfosuccinates , alkyl and alkenyl sulfos polyvalent metal salt of pyrithione can be used in combi uccinamates , alkyl and alkenyl ether sulfosuccinates , alkyl nation with a metal ion source such as copper and zinc salts , and alkenyl amidosulfosuccinates ; alkyl and alkenyl sul as disclosed in International Pat. Application Pub . No . WO phoacetates, alkyl and alkenyl phosphates, alkyl and alkenyl 01 /00151 , which is incorporated by reference for the perti ether phosphates, alkyl and alkenyl carboxylates , alkyl and nent disclosure therein . It is disclosed that antidandruff alkenyl ether carboxylates, alkyl and alkenyl amidoether efficacy can be dramatically increased in topical composi carboxylates , N - alkylamino acids , N - acyl amino acids , alkyl tions by the use of polyvalentmetal salts of pyrithione , such peptides , N -acyl taurates, acyl isethionates , carboxylate salts as ZPT, in combination with a metal ion source such as wherein the acyl group is derived from fatty acids , and the copper and zinc salts . The metal ion source may be selected alkali metal, alkaline earth metal, ammonium , amine, and from zinc , copper , silver , nickel, cadmium , mercury, and triethanolamine salts thereof. bismuth . In one aspect, the metal ion is selected from zinc [0164 ] In one aspect , the cation moiety of the forgoing salts , copper salts, silver salts, and mixtures thereof. salts is selected from sodium , potassium , magnesium , [ 0159 ] In one aspect, the metal ion is selected from zinc ammonium , mono -, di- and triethanolamine salts , and salts , copper salts , and mixtures thereof. Exemplary metal mono - , di- , and tri - isopropylamine salts . The alkyl and acyl ion salts of zinc and copper include , but are not limited to , groups of the foregoing surfactants contain from about 6 to zinc acetate , zinc oxide , zinc carbonate , zinc hydroxide , zinc about 24 carbon atoms in one aspect , from 8 to 22 carbon chloride, zinc sulfate, zinc citrate , zinc fluoride , zinc iodide , atoms in another aspect, and from about 12 to 18 carbon zinc lactate , zinc oleate , zinc oxalate , zinc phosphate , zinc atoms in a further aspect , and can be saturated or unsatu propionate , zinc salicylate , zinc selenate , zinc silicate , zinc rated . The aryl groups in the surfactants are selected from stearate , zinc sulfide , zinc tannate , zinc tartrate , zinc valer phenyl or benzyl. The ether containing surfactants set forth ate , zinc gluconate , zinc undecylate , and the like. Combi above can contain from 1 to 10 ethylene oxide and /or nations of zinc salts may also be used in the composition of propylene oxide units per surfactant molecule in one aspect , the disclosed technology Exemplary metal ion salts of and from 1 to 3 ethylene oxide units per surfactant molecule copper include, but are not limited to , copper disodium in another aspect. citrate , copper triethanolamine, copper carbonate , cuprous ammonium carbonate , cupric hydroxide , copper chloride, [0165 ] Examples of suitable anionic surfactants include cupric chloride , copper ethylenediamine complex , copper but are not limited to the sodium , potassium , lithium , oxychlon 'de , copper oxychloride sulfate , cuprous oxide , magnesium , ammonium , and triethanolamine lauryl sulfate , coco sulfate , tridecyl sulfate , myrstyl sulfate , cetyl sulfate , copper thiocyanate , and the like . Combinations of these cetearyl sulfate , stearyl sulfate , oleyl sulfate , and tallow copper salts may also be used in the composition of the sulfate ; the sodium , potassium , lithium , magnesium , and disclosed technology . ammonium salts of laureth sulfate , trideceth sulfate , myreth [0160 ] Themetal ion source is present in the composition sulfate , C12 -C13 pareth sulfate , C12 -C14 pareth sulfate , and in a ratio (wt . /wt . ) to polyvalent metal salt of pyrithione of C2- C15 pareth sulfate, ethoxylated with 1 , 2 , 3 , 4 or 5 moles from about 5 : 100 to about 5 : 1 in one aspect , from about 2 : 10 of ethylene oxide ; disodium lauryl sulfosuccinate , disodium to about 3 : 1 in another aspect, and from about 1 : 2 to about laureth sulfosuccinate , sodium cocoyl isethionate , sodium 2 : 1 in still another aspect . C2-C14 olefin sulfonate , sodium laureth -6 carboxylate , sodium methyl cocoyl taurate , sodium cocoyl glycinate , C . Detersive Surfactants sodium myristyl sarcocinate , sodium dodecylbenzene sul [0161 ] The surfactants utilized to formulate the hair care fonate , sodium cocoyl sarcosinate , sodium cocoyl gluta compositions of the disclosed technology are chosen from at m ate , potassium myristoyl glutamate , triethanolamine least one detersive surfactant selected from at least one monolauryl phosphate , and fatty acid soaps, including the US 2017 /0367963 A1 Dec . 28 , 2017 sodium , potassium , ammonium , and triethanolamine salts of Other non - limiting examples of suitable zwitterionic or a saturated and unsaturated fatty acids containing from about amphoteric surfactants are described in U . S . Pat. Nos . 8 to about 22 carbon atoms. 5 , 104 ,646 , and 5 , 106 , 609 . 0166 ] The anionic fatty acid soaps are salts of fatty acids [0171 ] Amino acid based surfactants suitable in the prac containing from about 8 to about 22 carbon atoms, and tice of the present technology include surfactants repre mixtures thereof. In another aspect, the fatty acid soap sented by the formula : contains from about 10 to about 18 carbon atoms, and mixtures thereof. In a further aspect, the fatty acid soap contains from about 12 to about 16 carbon atoms, and mixtures thereof. The fatty acids utilized in the soaps can be saturated and unsaturated and can be derived from synthetic R25 - N SC( O) M + sources, as well as from the hydrolysis of fats and natural oils . [0167 ] Exemplary saturated fatty acids include but are not wherein R25 represents a saturated or unsaturated hydrocar limited to octanoic , decanoic , lauric , myristic , pentade bon group having 10 to 22 carbon atoms or an acyl group canoic , palmitic , margaric , steric , isostearic , nonadecanoic , containing a saturated or unsaturated hydrocarbon group arachidic , behenic , and the like , and mixtures thereof. Exem having 9 to 22 carbon atoms, Y is hydrogen or methyl , Z is plary unsaturated fatty acids include but are not limited to selected from hydrogen , CH3, - CH (CH3 ) 2 , - CH2CH myristoleic , palmitoleic , oleic, linoleic , linolenic, and the ( CH3) 2 , CH ( CH , CH3CH4, CH?CH , like , and mixtures thereof. The fatty acids can be derived - CH CH ,OH , CH ,OH , CH ( OH )CH2 , ( CH ) from animal fat such as tallow , lard , poultry fat or from NH, ( CH , NHC( NH ) NH , CHUCKOO M * , vegetable sources such as coconut oil, red oil , palm kernel (CH2 ) 2C ( O ) O - M * . M is a salt forming cation . In one oil , palm oil , cottonseed oil , linseed oil, sunflower seed oil, aspect , R2 represents a radical selected from a linear or olive oil , soybean oil, peanut oil , corn oil, safflower oil , branched C10 to C22 alkyl group , a linear or branched C1o to sesame oil, rapeseed oil, canola oil, and mixtures thereof. C22 alkenyl group , an acyl group represented by R °C ( O ) - , [0168 ] The soap can be prepared by a variety of well wherein R2 is selected from a linear or branched Co to Cog known means such as by the direct base neutralization of a alkyl group , a linear or branched C , to Cz, alkenyl group . In fatty acid or mixtures thereof or by the saponification of one aspect, M * is a cation selected from sodium , potassium , suitable fats and vegetable oils or mixtures thereof with a ammonium , and the ammonium salt of mono - , di, and suitable base . Exemplary bases include potassium hydrox triethanolamine ( TEA ) . ide , potassium carbonate, sodium hydroxide and alkanol [0172 ] The amino acid surfactants can be derived from the alkylation and acylation of a - amino acids such as , for amines such as triethanolamine. Generally , the fat or oil is example , alanine , arginine, aspartic acid , glutamic acid , heated until liquefied and a solution of the desired base is glycine , isoleucine , leucine, lysine , phenylalanine, serine , added thereto . Soaps included in a composition utilized in tyrosine , and valine . Representative N -acyl amino acid the method of the disclosed technology can be made , for surfactants are , but not limited to the mono - and di - carboxy example , by a classic kettle process or modern continuous late salts ( e . g ., sodium , potassium , ammonium and TEA ) of manufacturing process wherein natural fats and oils such as N -acylated glutamic acid , for example , sodium cocoyl glu tallow or coconut oil or their equivalents are saponified with tamate , sodium lauroyl glutamate , sodium myristoyl gluta an alkali metal hydroxide using procedures well known to mate , sodium palmitoyl glutamate , sodium stearoyl gluta those skilled in the art . Alternatively , soaps can be made by mate , disodium cocoyl glutamate , disodium stearoyl the direct neutralization of free fatty acids such as lauric acid glutamate , potassium cocoyl glutamate , potassium lauroyl (C12 ), myristic acid (C14 ) , palmitic acid (C16 ), steric acid glutamate , and potassium myristoyl glutamate ; the carboxy (Cs ) , isostearic (Cs ) , and mixtures thereof, with an alkali late salts ( e . g ., sodium , potassium , ammonium and TEA ) of metal hydroxide or carbonate . N - acylated alanine, for example , sodium cocoyl alaninate , [0169 ] The anionic of the anionic surfactant component in and TEA lauroyl alaninate ; the carboxylate salts ( e . g . , the composition should be sufficient to provide the desired sodium , potassium , ammonium and TEA ) of N -acylated cleansing and lather performance, and generally ranges from glycine , for example , sodium cocoyl glycinate , and potas about 2 wt. % to about 50 wt. % in one aspect, from about sium cocoyl glycinate ; the carboxylate salts ( e . g . , sodium , 8 wt. % to about 30 wt. % in another aspect, from about 10 potassium , ammonium and TEA ) of N - acylated sarcosine, wt. % to about 25 wt. % in still another aspect, and from for example , sodium lauroyl sarcosinate , sodium cocoyl about 12 wt. % to about 22 wt. % in a further aspect, all sarcosinate, sodium myristoyl sarcosinate , sodium oleoyl weight percentages are based on the weight of the total sarcosinate , and ammonium lauroyl sarcosinate ; and mix composition . tures of the foregoing surfactants . 10170 ] The term “ amphoteric surfactant” as used herein , is [0173 ] The betaines and sultaines useful in the present also intended to encompass zwitterionic surfactants , which technology are selected from alkyl betaines, alkylamino are well known to formulators skilled in the art as a subset betaines , and alkylamido betaines , as well as the correspond of amphoteric surfactants . Non - limiting examples of ampho ing sulfobetaines ( sultaines) represented by the formulas: teric surfactants are disclosed McCutcheon ' s Detergents and Emulsifiers, North American Edition , supra, and McCutch eon ' s , Functional Materials , North American Edition , supra ; R28 R 28 both of which are incorporated by reference herein in their entirety . Suitable examples include but are not limited to R27 — N — R29 — AM + R27 — NHCH2 + N - R29 — AM amino acids ( e . g . , N - alkyl amino acids and N - acyl amino * R28* * ** 10 * * * acids ) , betaines , sultaines , and alkyl amphocarboxylates . US 2017 /0367963 A1 Dec . 28 , 2017 19

- continued typically have a hydrophobic portion , such as a long chain R28 alkyl group or an alkylated aryl group , and a hydrophilic portion containing various degrees of ethoxylation and /or R27 – & — NH - CH2 ) - NA - R29 - AM propoxylation ( e .g ., 1 to about 50 ) ethoxy and / or propoxy R28 moieties. Examples of some classes of nonionic surfactants that can be used include , but are not limited to , ethoxylated alkylphenols , ethoxylated and propoxylated fatty alcohols , wherein R27 is a C2- C22 alkyl or alkenyl group , each R28 polyethylene glycol ethers of methyl glucose , polyethylene independently is a C1- C4 alkyl group , R29 is a C -C5 alky glycol ethers of sorbitol, ethylene oxide -propylene oxide lene group or a hydroxy substituted C - C , alkylene group , n block copolymers , ethoxylated esters of fatty acids, conden is an integer from 2 to 6 , A is a carboxylate or sulfonate group , and M is a salt forming cation . In one aspect, R27 is sation products of ethylene oxide with long chain amines or a C1 - C18 alkyl group or a C11 - C18 alkenyl group . In one amides, condensation products of ethylene oxide with alco aspect , R28 is methyl. In one aspect , R29 is methylene , hols, and mixtures thereof. ethylene or hydroxy propylene . In one aspect, n is 3 . In a [0179 ] Suitable nonionic surfactants include, for example , further aspect, M is selected from sodium , potassium , mag alkyl polysaccharides, alcohol ethoxylates , block copoly nesium , ammonium , and mono - , di- and triethanolamine mers , castor oil ethoxylates , ceto / oleyl alcohol ethoxylates , cations . cetearyl alcohol ethoxylates, decyl alcohol ethoxylates, [0174 ] Examples of suitable betaines include , but are not dinonyl phenol ethoxylates, dodecyl phenol ethoxylates , limited to , lauryl betaine , coco betaine, oleyl betaine , coco end -capped ethoxylates , ether amine derivatives, ethoxy hexadecyl dimethylbetaine, coco dimethyl carboxymethyl lated alkanolamides, ethylene glycol esters , fatty acid betaine , lauryl dimethyl carboxymethyl betaine , cetyl dim alkanolamides, fatty alcohol alkoxylates , lauryl alcohol ethyl carboxymethyl betaine , lauryl amidopropyl betaine , ethoxylates, mono - branched alcohol ethoxylates, nonyl phe cocoamidopropyl betaine (CAPB ) , coco dimethyl sulfopro nol ethoxylates, octyl phenol ethoxylates , oleyl amine pyl betaine, stearyl dimethyl sulfopropyl betaine , lauryl ethoxylates , random copolymer alkoxylates, sorbitan ester dimethyl sulfoethyl betaine , and cocamidopropyl hydroxy ethoxylates , stearic acid ethoxylates , stearyl amine ethoxy sultaine . lates , tallow oil fatty acid ethoxylates , tallow amine ethoxy [ 0175 ]. The alkylamphocarboxylates such as the alkylam lates , tridecanol ethoxylates , acetylenic diols , polyoxyeth ylene sorbitols , and mixtures thereof. Various specific phoacetates and alkylamphopropionates (mono - and disub examples of suitable nonionic surfactants include , but are stituted carboxylates ) can be represented by the formula : not limited to , Cocamide MEA , Cocamide MIPA , methyl gluceth - 10 , PEG - 20 methyl glucose distearate , PEG - 20 methyl glucose sesquistearate , ceteth - 8 , ceteth - 12 , dodoxy R30 nol- 12 , laureth - 15 , PEG - 20 castor oil , polysorbate 20 , R27 - c NH - CH3 ) 2N = CH - CHORT steareth - 20, polyoxyethylene- 10 cetyl ether, polyoxyethyl ene- 10 stearyl ether, polyoxyethylene - 20 cetyl ether, poly oxyethylene - 10 oleyl ether , polyoxyethylene -20 oleyl ether, wherein R27 is a Cz -C22 alkyl or alkenyl group , R30 is an ethoxylated nonylphenol, ethoxylated octylphenol, - CH _ C (O )O - M * , — CH CH C (O )O - M * , or — CH . CH ethoxylated dodecylphenol, or ethoxylated fatty (Co - C22 ) (OH )CH2SO3 - M +, R3 is hydrogen or — CH C (O )O - M *, alcohol, including 3 to 20 ethylene oxide moieties, poly and M is a cation selected from sodium , potassium , mag oxyethylene -20 isohexadecyl ether, polyoxyethylene - 23 nesium , ammonium , and the ammonium salt of mono -, di glycerol laurate , polyoxyethylene - 20 glyceryl stearate , PPG and triethanolamine. 10 methyl glucose ether , PPG -20 methyl glucose ether, [ 0176 ] Exemplary alkylamphocarboxylates include , but polyoxyethylene -20 sorbitan monoesters , polyoxyethylene are not limited to , sodium cocoamphoacetate , sodium lau 80 castor oil , polyoxyethylene -15 tridecyl ether, polyoxy roamphoacetate , sodium capryloamphoacetate , disodium ethylene- 6 tridecyl ether, laureth - 2 , laureth - 3 , laureth - 4 , cocoamphodiacetate , disodium lauroamphodiacetate , diso PEG - 3 castor oil , PEG 600 dioleate, PEG 400 dioleate , dium caprylamphodiacetate , disodium capryloamphodiac poloxamers such as poloxamer 188 , polysorbate 21 , poly etate , disodium cocoamphodipropionate , disodium lauroam sorbate 40 , polysorbate 60 , polysorbate 61, polysorbate 65 , phodipropionate , disodium caprylamphodipropionate , and polysorbate 80 , polysorbate 81 , polysorbate 85 , sorbitan disodium capryloamphodipropionate . caprylate , sorbitan cocoate , sorbitan diisostearate , sorbitan (0177 ] The amount of such amphoteric or zwitterionic dioleate , sorbitan distearate , sorbitan fatty acid ester, sorbi detersive surfactants ranges from about 0 . 5 wt. % to about tan isostearate , sorbitan laurate , sorbitan oleate , sorbitan 20 wt. % in one aspect , and from about 1 wt. % to about 10 palmitate , sorbitan sesquiisostearate , sorbitan sesquioleate , wt. % in another aspect, based on the weight of the total sorbitan sesquistearate , sorbitan stearate , sorbitan triisoste composition . arate , sorbitan trioleate , sorbitan tristearate , sorbitan unde [ 0178 ] Non - limiting examples of nonionic surfactants are cylenate , or mixtures thereof. disclosed in McCutcheon ' s Detergents and Emulsifiers , [0180 ] Alkyl glycoside nonionic surfactants can also be North American Edition , 1998 , supra ; and McCutcheon ' s , employed and are generally prepared by reacting a mono Functional Materials , North American , supra ; both of which saccharide , or a compound hydrolyzable to a monosaccha are incorporated by reference herein in their entirety . Addi ride, with an alcohol such as a fatty alcohol in an acid tional Examples of nonionic surfactants are described in medium . For example , U . S . Pat . Nos . 5 ,527 ,892 and 5 , 770 , U . S . Pat. No . 4 , 285 , 841, to Barrat et al. , and U . S . Pat . No . 543 describe alkyl glycosides and /or methods for their 4 ,284 , 532 , to Leikhim et al. , both of which are incorporated preparation . Suitable examples are commercially available by reference herein in their entirety . Nonionic surfactants under the names of GlucoponTM 220 , 225 , 425 , 600 and 625 , US 2017 /0367963 A1 Dec . 28 , 2017

PLANTACARE® , and PLANTAPON® , all of which are on the weight of the total composition . The aqueous carrier available from Cognis Corporation . may comprise water, or a miscible mixture of water and [0181 ] In another aspect, nonionic surfactants include , but organic solvent, but preferably comprises water with mini are not limited to , alkoxylated methyl glucosides such as , for mal or no significant concentrations of organic solvent, example , methyl gluceth - 10 , methyl gluceth - 20 , PPG - 10 except as otherwise incidentally incorporated into the com methyl glucose ether , and PPG - 20 methyl glucose ether , position as minor ingredients of other essential or optional available from Lubrizol Advanced Materials , Inc. , under the components . trade names , Glucam® E10 , Glucam® E20 , Glucam® P10 , and Glucam® P20 , respectively ; and hydrophobically modi E . Optional Components fied alkoxylated methyl glucosides, such as PEG 120 methyl glucose dioleate , PEG - 120 methyl glucose trioleate , and [0188 ] The compositions of the present technology may PEG -20 methyl glucose sesquistearate , available from Lubr further comprise one or more optional components known izol Advanced Materials , Inc. , under the trade names , Glu for use in hair care or personal care products , provided that camate® DOE - 120 , GlucamateTM LT , and GlucamateTM the optional components are physically and chemically SSE - 20, respectively , are also suitable . Other exemplary compatible with the essential components described herein , hydrophobically modified alkoxylated methyl glucosides are or do not otherwise unduly impair product stability , aesthet disclosed in U . S . Pat. Nos. 6 , 573 , 375 and 6 ,727 , 357 , the ics or performance . Unless otherwise stated individual con relevant disclosure of which are hereby incorporated by centrations of such optional components may range from reference. about 0 . 001 wt. % to about 20 wt. % , based on the weight (0182 ) Other useful nonionic surfactants include water of the total composition . soluble silicones such as PEG - 10 Dimethicone , PEG - 12 [0189 ] Non -limiting examples of optional components for Dimethicone , PEG - 14 Dimethicone, PEG - 17 Dimethicone , use in the composition include insoluble or particulate PPG - 12 Dimethicone , PPG - 17 Dimethicone and deriva materials, conditioning agents (silicones , hydrocarbon oils , tized / functionalized forms thereof such as Bis - PEG /PPG fatty esters ) , auxiliary viscosity modifiers , humectants , sen 20 / 20 Dimethicone Bis - PEG /PPG - 16 / 16 PEG /PPG - 16 / 16 sates , botanicals , amino acids , vitamins , chelating agents , Dimethicone, PEG /PPG - 14 / 4 Dimethicone, PEG /PPG - 20 / buffering agents , pH adjusting agents , preservatives per 20 Dimethicone, PEG /PPG - 20 /23 Dimethicone , and Per fumes and fragrances , electrolytes , dyes and pigments , non fluorononylethyl Carboxydecyl PEG - 10 Dimethicone. volatile solvents or diluents (water soluble and insoluble ) , [0183 ] In one embodiment of the disclosed technology , at foam boosters , sunscreens and UV absorbers . least one anionic surfactant is utilized in combination with an amphoteric or zwitterionic surfactant. In one aspect, the 1 . Insoluble and Particulate Materials weight ratio (based on active material) of anionic surfactant ( non - ethoxylated and / or ethoxylated ) to amphoteric surfac [0190 ] In the compositions of the present technology, the tant can range from about 10 : 1 to about 2 : 1 in one aspect, nonionic , amphiphilic emulsion polymers of the disclosed and can be about 9 : 1 , about 8 : 1 , about 7 : 1 , about 6 : 1 , about technology can be utilized to enhance foaming properties, 5 : 1 , about 4 . 5 : 1 , about 4 : 1 , or about 3 : 1 in another aspect. improve mildness and the rheology properties of cleansing When employing an ethoxylated anionic surfactant in com compositions for the hair , scalp and skin , and can be utilized bination with a non - ethoxylated anionic surfactant and an for the stable suspension of insoluble silicones , opacifiers amphoteric or zwitterionic surfactant, the weight ratio and pearlescent agents ( e . g . , mica , coated mica , ethylene (based on active material) of ethoxylated anionic surfactant glycol monostearate ( EGMS ) , ethylene glycol distearate to non - ethoxylated anionic surfactant to amphoteric surfac ( EGDS ) , polyethylene glycol monostearate (PGMS ) or tant can range from about 3 . 5 : 3 . 5 : 1 in one aspect to about polyethyleneglycol distearate (PGDS ) ) , pigments , exfoli 1 : 1 : 1 in another aspect. ants , auxiliary anti - dandruff agents , clay, swellable clay , [ 0184 ] In one aspect, the anionic surfactant is selected laponite , gas bubbles , liposomes , microsponges, cosmetic from alkyl sulfates , including sodium lauryl sulfate , ammo beads, cosmetic microcapsules, and flakes , and are discussed nium lauryl sulfate , sodium coco - sulfate , and mixtures in more detail below . thereof. [0191 ] Exemplary cosmetic bead components include, but [ 0185 ] In one aspect, the anionic surfactant is selected are not limited to , agar beads, alginate beads, jojoba beads, from ethoxylated alkyl sulfates including sodium laureth gelatin beads , StyrofoamTM beads, polyacrylate , polymeth sulfate , ammonium laureth sulfate , sodium trideceth sulfate , ylmethacrylate (PMMA ) , polyethylene beads, UnispheresTM and mixtures thereof . and UnipearlsTM cosmetic beads ( Induchem USA , Inc ., New [ 0186 ] In one aspect, the optional amphoteric surfactant is York , N . Y . ) , LipocapsuleTM , LiposphereTM , and LipopearlTM selected from alkyl betaines , amidoalkyl betaines and ami microcapsules (Lipo Technologies Inc. , Vandalia , Ohio ), and doalkyl sultaines including lauryl betaine , cocamidopropy1 Confetti IITM dermal delivery flakes (United -Guardian , Inc . , betaine, cocamidopropyl hydroxysultaine , and mixtures Hauppauge , N . Y . ) . Beads can be utilized as aesthetic mate thereof. rials or can be used to encapsulate benefit agents to protect them from the deteriorating effects of the environment or for D . Aqueous Carrier optimal delivery , release and performance in the final prod [0187 ] The compositions of the present technology are uct. typically in the form of pourable liquids (under ambient [0192 ] In one aspect, the cosmetic beads range in size conditions ) . The compositions will therefore typically com from about 0 . 5 to about 1 . 5 mm . In another aspect, the prise an aqueous carrier, which is present at a level of from difference in specific gravity of the bead and water is about 20 wt. % to about 95 wt. % in one aspect , and from between about + / - 0 .01 and 0 . 5 in one aspect, and from about about 60 wt. % to about 85 wt. % in another aspect, based + - 0 . 2 to 0 . 3 g /ml in another aspect. US 2017 /0367963 A1 Dec . 28 , 2017 21

[0193 ] In one aspect, themicrocapsules range in size from lalkylsiloxanes , amino functional polyalkylsiloxanes, qua about 0 . 5 to about 300 um . In another aspect , the difference ternary functional polyalkylsiloxanes, and mixtures thereof. in specific gravity between the microcapsules and water is F0198 ] In one aspect , the silicone oil conditioning agent from about + / - 0 .01 to 0 . 5 . Non - limiting examples of micro includes polyorganosiloxanes represented by the formula : capsule beads are disclosed in U . S . Pat. No . 7 ,786 , 027 , the disclosure of which is herein incorporated by reference . R40R40 [ R40 1 RR40 40 2 . Conditioning Agents B — $ i — o + si - o + $ i — B [0194 ] Conditioning agents include any material which is used to give a particular conditioning benefit to hair, scalp R40 [ R40 J , R40 and / or skin . In hair treatment compositions , suitable condi tioning agents are those which deliver one or more benefits wherein B independently represents hydroxy , methyl, relating to shine, softness , combability , antistatic properties , methoxy, ethoxy, propoxy, and phenoxy ; R40 independently wet- handling , damage, manageability , body, and greasiness. represents methyl, ethyl, propyl, phenyl, methylphenyl , phe The conditioning agents useful in the compositions of the nylmethyl, a primary, secondary or tertiary amine , a quater present technology typically comprise a water insoluble , nary group selected from a group selected from : water dispersible , non -volatile , liquid that forms emulsified , [0199 ] - R41 _ N (R42 ) CH CH _N (R42 ) z; liquid particles . Suitable conditioning agents for use in the [0200 ] - R41 — N (R42 ) z; composition are those conditioning agents characterized [0201 ] - R41 — N + (R42 ) ,CA " ; and generally as silicones ( e . g ., silicone oils , cationic silicones , [0202 ] - R41 _ N (R42 )CH2CH2N +( R42 ) H , CA ; silicone gums, high refractive silicones , and silicone resins ), wherein R41 is a linear or branched , hydroxyl substituted or organic conditioning oils (e .g . , hydrocarbon oils , polyole unsubstituted alkylene or alkylene ether moiety containing 2 fins , and fatty esters ) or combinations thereof, or those to 10 carbon atoms; R42 is hydrogen , C . -C20 alkyl (e .g , conditioning agents which otherwise form liquid , dispersed methyl) , phenyl or benzyl; q is an integer ranging from about particles in the aqueous surfactant matrix herein . Such 2 to about 8 ; CA - is a halide ion selected from chlorine , conditioning agents should be physically and chemically bromine , iodine and fluorine; and x is an integer ranging compatible with the essential components of the composi from about 7 to about 8000 in one aspect , from about 50 to tion , and should not otherwise unduly impair product sta about 5000 in another aspect, form about 100 to about 3000 bility , aesthetics or performance . in still another aspect, and from about 200 to about 1000 in a further aspect . Silicones [0203 ]. In one aspect, the amino functional polyalkylsilox [0195 ] The silicone conditioning agent may comprise ane can be represented by the formula : volatile silicones, non - volatile silicones , and mixtures thereof. If volatile silicones are present, they are typically employed as a solvent or carrier for commercially available CH3 CH3 CH3 CH3 forms of non - volatile silicone fluid conditioning agents such B - Sito Si 1 0 - Si - O - S B as oils and gums and resins . Volatile silicone fluids are often included in the conditioning package to improve silicone CH3 L CH3 CH3 fluid deposition efficacy or to enhance the shine, sheen or glossiness of the hair . Volatile silicone materials are fre quently included in formulations to enhance sensory attri wherein B independently represents hydroxy, methyl, butes ( e . g ., feel ) on the hair, scalp and skin methoxy , ethoxy, propoxy, and phenoxy ; and R4° is selected [0196 ] In one aspect, the silicone conditioning agent is from : non - volatile and includes silicone oils , gums, resins and [0204 ] - R41 — N (R42 ) CH ,CH , N (R42 ) z ; mixtures thereof . By non -volatile is meant that the silicone [0205 ] - R41 _ N (R42 ) ; has a very low vapor pressure at ambient temperature [ 0206 ] - R41 — N + (R42 ) , CA ; and conditions ( e . g . , less than 2 mm Hg at 20° C . ). The non [ 0207] R41 _ N ( R2) CH , CHUN * ( R ^2H , CA volatile silicone conditioning agent has a boiling point above wherein R4! is a linear or branched , hydroxyl substituted or about 250° C . in one aspect, above about 260° C . in another unsubstituted alkylene or alkylene ether moiety containing 2 aspect, and above about 275º C . in a further aspect . Back to 10 carbon atoms; R42 is hydrogen , C . - C20 alkyl ( e. g , ground information on silicones including sections discuss methyl ), phenyl or benzyl ; CA is a halide ion selected from ing silicone oils , gums, and resins , as well as their manu chlorine , bromine , iodine and fluorine ; and the sum of m + n facture , are found in Encyclopedia of Polymer Science and ranges from about 7 to about 1000 in one aspect, from about Engineering , vol. 15 , 2d ed ., pp 204 - 308 , John Wiley & 50 to about 250 in another aspect, and from about 100 to about 200 in another aspect, subject to the proviso that m or Sons, Inc. ( 1989 ) . n is not 0 . In one aspect B is hydroxy and R40 is — (CH , ) 3NH (CH2 ) 2NH2. In another aspect B is methyl and R40 is Silicone Oil ( CH2) 2NH (CH2 ) 2NH2. In still another aspect B is methyl [0197 ] In one aspect, the silicone conditioning agent is and R40 is a quaternary ammonium moiety represented by silicone oil selected from a polyorganosiloxane material. In ( CH2) 2OCH CH (OH ) CH N (R42 ) 3 CA ; wherein R42 and one aspect , the polyorganosiloxane material can be selected CA are as previously defined from polyalkylsiloxanes , polyarylsiloxanes, polyalkylaryl- (0208 ] The silicone oil conditioning agents can have a siloxanes, hydroxyl terminated polyalkylsiloxanes, polyary viscosity ranging from about above about 25 to about US 2017 /0367963 A1 Dec . 28 , 2017

1 ,000 ,000 mPa .s at 25° C . in one aspect, from about 100 to crosslinking in a particular silicone material . Silicone mate about 600 , 000 mPa. s in another aspect, and from about 1000 rials which have at least about 1 . 1 oxygen atoms per silicon to about 100 , 000 mPa . s still another aspect, from about atom will generally be silicone resins herein . In one aspect, 2 , 000 to about 50 ,000 mPa . s in yet another aspect, and from the ratio of oxygen :silicon atoms is at least about 1 . 2 : 1 . 0 . about 4 , 000 to about 40 , 000 mPa . s in a further aspect . The Silanes used in the manufacture of silicone resins include viscosity is measured by means of a glass capillary viscom monomethyl- , dimethyl - , trimethyl - , monophenyl - , diphe eter as described by Dow Corning Corporate Test Method nyl - ,methylphenyl - ,monovinyl - , and methylvinyl - chlorosi CTM004, dated Jul. 20 , 1970 . In one aspect the silicone oils lanes , and terachlorosilane , with the methyl substituted have an average molecular weight below about 200 ,000 silanes being most commonly utilized . daltons . The average molecular weight can typically range (0213 ] Silicone materials and silicone resins can be iden from about 400 to about 199 ,000 daltons in one aspect, from tified according to a shorthand nomenclature system known about 500 to about 150 , 000 daltons in another aspect, from to those of ordinary skill in the art as “MDTQ ” nomencla about 1 , 000 to about 100 , 000 daltons in still another aspect, ture . Under this naming system , the silicone is described from about 5 , 000 to about 65 ,000 daltons in a further aspect. according to the presence of various siloxane monomer units [0209 ] Exemplary silicone oil conditioning agents which make up the silicone . The “ MDTQ ” nomenclature include, but are not limited to , polydimethylsiloxanes ( dime system is described in the publication entitled “ Silicones : thicones ), polydiethylsiloxanes, polydimethyl siloxanes Preparation , Properties and Performance ” ; Dow Corning having terminal hydroxyl groups (dimethiconols ) , polym Corporation , 2005 , and in U . S . Pat . No . 6 ,200 ,554 . ethylphenylsiloxanes , phenylmethylsiloxanes , amino func [02141 Exemplary silicone resins for use in the composi tional polydimethylsiloxanes ( amodimethicones) , and mix tions of the disclosed technology include , but are not limited tures thereof. to MQ , MT, MTQ , MDT and MDTQ resins. In one aspect , methyl is the silicone resin substituent. In another aspect, the Silicone Gum silicone resin is selected from a MQ resins, wherein the M : Q ratio is from about 0 . 5 : 1 . 0 to about 1 . 5 : 1 . 0 and the average [0210 ] Another silicone conditioning agent useful in the molecular weight of the silicone resin is from about 1000 to disclosed technology is a silicone gum . A silicone gum is a polyorganosiloxane material of the same general structure of about 10 ,000 daltons . the silicone oils set forth above wherein B independently represents hydroxy , methyl, methoxy , ethoxy , propoxy , and Volatile Silicones phenoxy ; R *' independently represents methyl, ethyl, pro [0215 ] The optional volatile silicones referred to above pyl, phenyl, methylphenyl, phenylmethyl , and vinyl . Sili include linear polydimethylsiloxanes and cyclic polydim cone gums have a viscosity measured at 25° C . of greater ethylsiloxanes (cyclomethicones ) , and mixtures thereof. than 1 ,000 , 000 mPa. s . The viscosity can be measured by Volatile linear polydimethylsiloxanes ( dimethicones ) typi means of a glass capillary viscometer as described above for cally contain about 2 to about 9 silicon atoms, alternating the silicone oils . In one aspect the silicone gums have an with oxygen atoms in a linear arrangement. Each silicon average molecular weight about 200 , 000 daltons and above . atom is also substituted with two alkyl groups (the terminal The molecular weight can typically range from about 200 , silicon atoms are substituted with three alkyl groups) , such 000 to about 1 ,000 , 000 daltons. It is recognized that the as, for example , methyl groups. The cyclomethicones typi silicone gums described herein can also have some overlap cally contain about 3 to about 7 dimethyl substituted silicon with the silicone oils described previously. This overlap is atoms in one aspect and from about 3 to about 5 in another not intended as a limitation on any of these materials . aspect, alternating with oxygen atoms, in a cyclic ring [ 0211 ] Suitable silicone gums for use in the silicone com structure . The term “ volatile ” means that the silicone has a ponent of compositions of the disclosed technology are measurable vapor pressure , or a vapor pressure of at least 2 polydimethylsiloxanes (dimethicones ) , optionally having mm of Hg at 20° C . The volatile silicones have a viscosity terminal end groups such as hydroxyl (dimethiconols ), of 25 mPa . s or less at 25° C . in one aspect , from about 0 .65 polymethylvinylsiloxane, polydiphenylsiloxane, and mix about to about 10 mPa .s in another aspect, from about 1 to about 5 mPa . s in still another aspect , and from about 1 . 5 to tures thereof. about 3 . 5 mPa. s in a further aspect . A description of linear and cyclic volatile silicones is found in Todd and Byers , Silicone Resins “ Volatile Silicone Fluids for Cosmetics” , Cosmetics and [0212 ] Silicone resins can be included as a silicone con Toiletries, Vol. 91 ( 1 ), pp . 27 - 32 (1976 ), and in Kasprzak , ditioning agent suitable for use in the compositions of the “ Volatile Silicones ” , Soap / Cosmetics /Chemical Specialities , disclosed technology . These resins are crosslinked polysi pp . 40 - 43 ( December 1986 ) . loxanes . The crosslinking is introduced through the incor [0216 ] Exemplary volatile linear dimethicones include , poration of trifunctional and tetrafunctional silanes with but are not limited to , hexamethyldisiloxane , octamethyl monofunctional and /or difunctional silanes during manufac trisiloxane , decamethyltetrasiloxane, dodecamethylpentasi ture of the silicone resin . As is well understood in the art , the loxane and blends thereof. Volatile linear dimethicones and degree of crosslinking that is required in order to result in a dimethicone blends are commercially available from Dow silicone resin will vary according to the specific silane units Corning Corporation as Dow Corning 200® Fluid ( e . g ., incorporated into the silicone resin . In general, silicone product designations 0 .65 CST , 1 CST , 1 . 5 CST, and 2 CST) materials which have a sufficient level of trifunctional and and Dow Corning® 2 -1184 Fluid . tetra -functional siloxane monomer units ( and hence , a suf [0217 ] Exemplary volatile cyclomethicones are D4 ficient level of crosslinking ) such that they form a rigid or cyclomethicone (octamethylcyclotetrasiloxane ) , D5 hard film are considered to be silicone resins . The ratio of cyclomethicone (decamethylcyclopentasiloxane ) , D6 oxygen atoms to silicon atoms is indicative of the level of cyclomethicone , and blends thereof ( e . g ., D4/ D5 and US 2017 /0367963 A1 Dec . 28 , 2017 22

D5 /D6 ) . Volatile cyclomethicones and cyclomethicone [0223 ] Fluorinated or perfluorinated oils are also contem blends are commercially available from Momentive Perfor plated within the scope of the present technology. Fluori mance Materials Inc . as SF1173 , SF1202 , SF1256 , and nated oils include perfluoropolyethers described in Euro SF1258 silicone fluids , and Dow Corning Corporation as pean Patent 0 486 135 and the fluorohydrocarbon Dow Corning® 244 , 245 , 246 , 345 , and 1401 silicone fluids. compounds described in WO 93 / 11103 . The fluoridated oils Blends of volatile cyclomethicones and volatile linear dime may also be fluorocarbons such as fluoramines, e .g ., per thicones also can be employed . fluorotributylamine , fluoridated hydrocarbons, such as per [0218 ] The amount of silicone conditioner( s ) in the com fluorodecahydronaphthalene , fluoroesters , and fluoroethers . positions of the present technology should be sufficient to provide the desired conditioning performance to the hair , Natural Oils and generally ranges from about 0 .01 to about 20 wt. % in [0224 ] Natural oil conditioners are also useful in the one aspect, from about 0 . 05 to about 15 wt. % in another practice of the disclosed technology and include but are not aspect, from about 0 . 1 % to about 10 wt. % in still another limited to peanut, sesame, avocado , coconut, cocoa butter , aspect , and from about 1 to about 5 wt. % in a further aspect , almond , safflower, corn , cotton seed , sesame seed , walnut based on the total weight of the composition . oil, castor, olive , jojoba , palm , palm kernel, soybean , wheat germ , linseed , sunflower seed ; eucalyptus , lavender, vetiver, Hydrocarbon Oils litsea , cubeba , lemon , sandalwood , rosemary , chamomile , [ 0219] The conditioning component of the compositions savory , nutmeg , cinnamon , hyssop , caraway , orange , gera of the disclosed technology can also contain hydrocarbon oil nium , cade, and bergamot oils , fish oils , glycerol tricapro conditioners . caprylate ; and mixtures thereof. [ 0220 ] Suitable conditioning oils for use as conditioning agents in the compositions of the disclosed technology Ester Oils include , but are not limited to , hydrocarbon oils having at [0225 ] Ester oil conditioners include, but are not limited least about 10 carbon atoms, such as cyclic hydrocarbons, to , fatty esters having at least 10 carbon atoms . These fatty straight chain aliphatic hydrocarbons ( saturated or unsatu esters include esters derived from fatty acids or alcohols rated ), and branched chain aliphatic hydrocarbons ( saturated ( e . g . , mono - esters , polyhydric alcohol esters , and di- and or unsaturated ), including polymers and mixtures thereof. tri -carboxylic acid esters) . The fatty esters hereof may Straight chain hydrocarbon oils typically contain about 12 to include or have covalently bonded thereto other compatible 19 carbon atoms. Branched chain hydrocarbon oils , includ functionalities, such as amides and alkoxy moieties ( e . g . , ing hydrocarbon polymers, typically will contain more than ethoxy or ether linkages , etc . ) . 19 carbon atoms. [0226 ] Exemplary fatty esters include , but are not limited [0221 ] Specific non - limiting examples of these hydrocar to isopropyl isostearate , hexyl laurate , isohexyl laurate , bon oils include paraffin oil, mineral oil , saturated and isohexyl palmitate , isopropyl palmitate , decyl oleate , isode unsaturated dodecane, saturated and unsaturated tridecane , cyl oleate , hexadecyl stearate , decyl stearate , isopropyl saturated and unsaturated tetradecane , saturated and unsatu isostearate, dihexyldecyl adipate , lauryl lactate , myristyl rated pentadecane, saturated and unsaturated hexadecane , lactate , cetyl lactate, oleyl stearate , oleyl oleate , oleyl polybutene, polydecene, and mixtures thereof . Branched myristate , lauryl acetate , cetyl propionate , and oleyl adipate . chain isomers of these compounds , as well as of higher chain [0227 ] Other fatty esters suitable for use in the composi length hydrocarbons, can also be used , examples of which tions of the disclosed technology are mono - carboxylic acid include highly branched , saturated or unsaturated , alkanes esters of the general formula R °C ( O )OR?1 , wherein RC such as the permethyl- substituted isomers , e .g ., the perm and Rºl are alkyl or alkenyl radicals , and the sum of carbon ethyl- substituted isomers of hexadecane and eicosane , such atoms in Rºº and Rºis at least 10 in one aspect , and at least as 2 ,2 ,4 , 4 ,6 ,6 , 8 ,8 - dimethyl- 10 -methylundecane and 2 ,2 ,4 , 4 , 22 in another aspect of the disclosed technology. 6 ,6 -dimethyl - 8 -methylnonane , available from Permethyl [0228 ] Still other fatty esters suitable for use in the com Corporation . Hydrocarbon polymers such as polybutene and positions of the disclosed technology are di- and tri -alkyl polydecene . A preferred hydrocarbon polymer is poly and alkenyl esters of carboxylic acids, such as esters of C4 butene , such as the copolymer of isobutylene and butene. A to Cg dicarboxylic acids ( e . g . , C , to C22 esters , preferably C commercially available material of this type is L - 14 poly to C . , of succinic acid , glutaric acid , adipic acid ) . Specific butene from BP Chemical Company . non - limiting examples of di- and tri -alkyl and alkenyl esters [ 0222] Liquid polyolefin conditioning oils can be used in of carboxylic acids include isocetyl stearyol stearate, diiso the hair straightening compositions of the present technol propyl adipate , and tristearyl citrate. ogy. The liquid polyolefin conditioning agents are typically [0229 ] Other fatty esters suitable for use in the composi poly - a -olefins that have been hydrogenated . Polyolefins for tions of the disclosed technology are those known as poly use herein can be prepared by the polymerization of C4 to hydric alcohol esters . Such polyhydric alcohol esters include about C14 olefinic monomers . Non -limiting examples of alkylene glycol esters, such as ethylene glycol mono and olefinic monomers for use in preparing the polyolefin liquids di- fatty acid esters , diethylene glycol mono - and di- fatty herein include ethylene, propylene , 1 -butene , 1 - pentene , acid esters , polyethylene glycol mono - and di- fatty acid 1 -hexene , 1 - octene , 1 -decene , 1 - dodecene , 1 -tetradecene , esters , propylene glycol mono - and di- fatty acid esters , branched chain isomers such as 4 -methyl - 1 - pentene, and polypropylene glycol monooleate , polypropylene glycol mixtures thereof. In one aspect of the disclosed technology , 2000 monostearate , ethoxylated propylene glycol monoste hydrogenated a - olefin monomers include , but are not lim arate , glyceryl mono - and di- fatty acid esters , polyglycerol ited to : 1 - hexene to 1 -hexadecenes , 1 -octene to 1 - tetrade poly -fatty acid esters, ethoxylated glyceryl monostearate , cene, and mixtures thereof. 1 , 3 -butylene glycol monostearate , 1 , 3 -butylene glycol dis US 2017 /0367963 A1 Dec . 28 , 2017 24

tearate , polyoxyethylene polyol fatty acid ester, sorbitan ammonium moiety contains one C , to C2 , alkyl group , and fatty acid esters , and polyoxyethylene sorbitan fatty acid three C , to C5 alkyl groups ( e . g ., methyl, ethyl, propyl , butyl esters . and pentyl, and combinations thereof ) . In one aspect , the [ 0230 ] Specific non -limiting examples of suitable syn quaternary ammonium moiety contains one C12 to C22 alkyl thetic fatty esters include: P - 43 (Cg to C10 triester of trim group , and two C , to C5 alkyl groups ( e . g . , methyl, ethyl, ethylolpropane ) , MCP - 684 (tetraester of 3 , 3 diethanol - 1, 5 propyl, butyl and pentyl, and combinations thereof) , and one pentadiol) , MCP 121 ( Cg to C10 diester of adipic acid ), all of moiety containing an alkoxy ; polyoxyalkylene ( e. g ., poly which are available from ExxonMobil Chemical Company. ethylene, polypropylene, and combinations thereof) , where [0231 ] The amount of hydrocarbon and natural condition the polyoxyalkylene moiety contains 3 to 100 repeating ing oils and ester oil conditioning agents can range from units ; acetamide; alkylamido ; alkylamidoalkyl; hydroxy about 0 .05 to about 10 wt. % , in one aspect, from about 0 . 5 alkyl; aryl; araalkyl ; or alkylaryl group having 1 to about 22 to about 5 wt. % in another aspect , and from about 1 to about carbon atoms in the alkyl chain , and having 6 to about 14 3 wt. % in a further aspect , based on the total weight of the carbon atoms in the aryl moiety . composition . [0236 ] A number of quaternary nitrogen - containing com pounds and polymers , their manufacturers and general Cationic Compounds and Polymers descriptions of their chemical characteristics are found in the [ 0232 ] Cationic Compounds refer to non -polymeric and CTFA Dictionary and in the International Cosmetic Ingre polymeric compounds containing at least one cationic moi dient Dictionary , Vol. 1 and 2 , 5th Ed ., published by the ety or at least one moiety that can be ionized to form a Cosmetic Toiletry and Fragrance Association , Inc . (CTFA ) cationic moiety . Typically these cationic moieties are nitro ( 1993 ) , the pertinent disclosures of which are incorporated gen containing groups such as quaternary ammonium or herein by reference . The name assigned to the ingredients by protonated amino groups . The cationic protonated amines the CTFA or by the manufacturer is used for convenience . can be primary , secondary , or tertiary amines . In one aspect , [ 0237 ] Non -limiting examples of monomeric quaternary the cationic conditioning compounds include quaternary ammonium compounds useful as cationic conditioners in the nitrogen containing non -polymeric and polymeric materials present technology include Acetamidopropyl Trimonium that well known in the art for hair conditioning. Cationic Chloride , Behenamidopropyl Ethyldimonium Ethosulfate , conditioning compounds include non - polymeric compounds Behentrimonium Chloride, Behentrimonium Methosulfate , containing one quaternary ammonium saltmoiety and poly CetethylMorpholinium Ethosulfate , Cetrimonium Chloride , meric compounds (polymers ) containing at least one qua Cocoamidopropyl Ethyldimonium Ethosulfate , Dicetyldi ternary ammonium salt moiety . monium Chloride , Hydroxyethyl Behenamidopropyl Dimo [ 0233 ] In one aspect , the quaternary ammonium salt moi nium Chloride , Quaternium - 26 , Quaternium -27 , Quater ety corresponds to the general formula : (R70 ) (R71 ) ( R72 ) nium -53 , Quaternium -63 , Quaternium - 70 , Quaternium - 72 , (R73 ) N + ) E where each of R70 , R7 , R74 , and R75 are Quaternium - 76 PPG - 9 Diethylmonium Chloride , PPG -25 independently selected from an aliphatic group having from Diethylmonium Chloride , PPG -40 Stearalkonium Chloride, 1 to about 22 carbon atoms ( e. g . , alkyl, alkenyl) ; an aromatic ( e . g ., phenyl benzyl ) ; alkoxy ; polyoxyalkylene ( e . g ., poly Isostearamidopropyl Ethyldimonium Ethosulfate , and mix ethylene , polypropylene, and combinations thereof) ; acet tures thereof. amido ; alkylamido ; alkylamidoalkyl; hydroxyalkyl; aryl; [0238 ] Cationic polymers are also useful as conditioning araalkyl; or alkylaryl group having 1 to about 22 carbon agents alone or in combination with the other conditioning atoms in the alkyl chain ; and E is a salt - forming anion such agents described herein . Suitable cationic polymers can be as those selected from halogen , ( e .g ., chloride , bromide ) , synthetically derived or natural polymers can be syntheti acetate , citrate , lactate , glycolate , phosphate , nitrate , sulfate , cally modified to contain cationic moieties. Polymeric qua and alkylsulfate ( e . g ., methosulfate , ethosulfate ). The ali ternary ammonium moiety salt containing polymers can be phatic groups can contain , in addition to carbon and hydro prepared by the polymerization of a diallylamine such as gen atoms, ether linkages , ester linkages, and other groups dialkyldiallylammonium salt or copolymer thereof in which such as amino groups . The longer chain aliphatic groups, the alkyl group contains 1 to about 22 carbon atoms in one e . g ., those of about 12 carbons, or higher , can be saturated aspect and methyl or ethyl in another aspect . Copolymers or unsaturated . Any two of R70 , R71 , R74 , and R75 together containing a quaternary moiety derived from a dialkyldial with the nitrogen atom to which they are attached can be lylammonium salt and an anionic component derived from taken together to form a ring structure containing 5 to 6 anionic monomers of acrylic acid and methacrylic acid are carbon atoms, one of said carbon atoms can optionally be suitable conditioning agents . Also suitable are , polyampho replaced with a heteroatom selected from nitrogen , oxygen lyte terpolymers having a cationic component prepared from or sulfur. a derivative of diallylamine, such as a dimethyldiallylam [0234 ] In one aspect , the quaternary ammonium moiety monium salt, an anionic component derived from anionic contains at least one nitrogen atom that is covalently linked monomers of acrylic acid or 2 - acrylamido - 2 -methylpropane to at least three alkyl and / or aryl substituents , and the sulfonic acid and a nonionic component derived from non nitrogen atom remains positively charged regardless of the ionic monomers of acrylamide . The preparation of such environmental pH . quaternary ammonium salt moiety containing polymers can [ 0235 ] In one aspect, the quaternary ammonium moiety be found , for example , in U . S . Pat. Nos . 3 , 288 , 770 ; 3 ,412 , contains one nitrogen atom and at least one C12 to C22 alkyl 019 ; 4 , 772 , 462 and 5 ,275 ,809 , the pertinent disclosures of group . In one aspect , the quaternary ammonium moiety which are incorporated herein by reference . contains one C12 to C22 alkyl group and at least two C , to C [0239 ] In one aspect , suitable cationic polymers include alkyl groups ( e .g ., methyl, ethyl, propyl , butyl and pentyl, the chloride salts of the foregoing quaternized homopoly and combinations thereof ). In one aspect , the quaternary mers and copolymers in which the alkyl group is methyl or US 2017 /0367963 A1 Dec . 28 , 2017 25

ethyl, and are commercially available under the Merquat® potato starch having the CTFA name, Starch Hydroxypro series of trademarks from Lubrizol AdvancedMaterials , Inc . pyltrimonium Chloride , is available under the SensomerTM [ 0240 ] A homopolymer prepared from diallyl dimethyl CI- 50 trademark , from Lubrizol Advanced Materials , Inc . ammonium chloride (DADMAC ) having the CTFA name, [0244 ] Other suitable cationically modified natural poly Polyquaternium - 6 , is available under the Merquat 100 and mers include cationic polygalactomannan derivatives such Merquat 106 trademark . A copolymer prepared from as guar gum derivatives and cassia gum derivatives , e . g . , DADMAC and acrylamide having the CTFA name, Poly CTFA : Guar Hydroxypropyltrimonium Chloride , Hydroxy quaternium - 7 , is sold under the Merquat 550 trademark . propylGuar Hydroxypropyltrimonium Chloride , and Cassia Another copolymer prepared from DADMAC and acrylic Hydroxypropyltrimonium Chloride. Guar hydroxypropylt acid having the CTFA name, Polyquaternium - 22 , is sold rimonium chloride is commercially available under the under the Merquat 280 trademark . The preparation of Poly JaguarTM trade name series from Rhodia Inc . and the quaternium - 22 and its related polymers is described in U . S . N - Hance trade name series from Ashland Inc. Cassia Pat. No. 4 ,772 , 462, the pertinent disclosures of which are Hydroxypropyltrimonium Chloride is commercially avail incorporated herein by reference . able under the SensomerTM CT- 250 and SensomerTM CT- 400 [ 0241 ] Also useful is an ampholytic terpolymer prepared trademarks from Lubrizol Advanced Materials , Inc. from a nonionic component derived from acrylamide or [0245 ] The non -polymeric and polymeric cationic com methyl acrylate , a cationic component derived from pounds can be present from about 0 . 05 to about 5 wt. % DADMAC or methacrylamidopropyl trimethyl ammonium percent in one aspect, from about 0 . 1 to about 3 wt. percent chloride (MAPTAC ), and an anionic component derived in another aspect , and from about 0 . 5 to about 2 . 0 wt. % in from acrylic acid or 2 -acrylamido - 2- methylpropane sulfonic a further aspect (based on the total weight of the composi acid or combinations of acrylic acid and 2 -acrylamido - 2 tion ) . methylpropane sulfonic acid . An ampholytic terpolymer prepared from acrylic acid , DADMAC and acrylamide hav Auxiliary Viscosity Modifier ing the CTFA name , Polyquarternium -39 , is available under the Merquat Plus 3330 trademark . Another ampholytic ter [0246 ] The composition of the disclosed technology must polymer prepared from acrylic acid , methacrylamidopropyl be easily pourable with a shear thinning index of less than trimethyl ammonium chloride (MAPTAC ) and methyl acry 0 . 5 at shear rates between 0 . 1 and 1 reciprocal second , and late having the CTFA name, Polyquarternium - 47 , is avail an optical transmission of at least 10 % . The suspension able under the Merquat 2001 trademark . Still another agent of the disclosed technology optionally can be utilized ampholytic terpolymer prepared from acrylic acid , MAP in combination with an auxiliary rheology modifier ( thick TAC and acrylamide having the CTFA name, Polyquarter ener ) to enhance the yield value of a thickened liquid . In one nium -53 , is available under the Merquat 2003PR trademark . aspect , the nonionic , amphiphilic emulsion , emulsion poly The preparation of such terpolymers is described in U . S . Pat. mer of the disclosed technology can be combined with a No . 5 , 275 , 809 , the pertinent disclosures of which are incor nonionic rheology modifier to enhance the yield stress value porated herein by reference . of a composition in which it is included . Any rheology [ 0242] Other cationic polymers and copolymers suitable modifier is suitable , so long as such is soluble in water, as conditioners in the hair straightening compositions of the stable and contains no ionic or ionizable groups . Suitable disclosed technology have the CTFA names Polyquater rheology modifiers include , but are not limited to natural nium - 4 , Polyquaternium - 11 , Polyquarternium - 16 , Poly gums ( e . g ., polygalactomannan gums selected from fenu quaternium -28 , Polyquaternium - 29 , Polyquaternium -32 , greek , cassia , locust bean , tara and guar ), modified cellulose Polyquaternium - 33 , Polyquaternium - 35 , Polyquaternium ( e . g ., ethylhexylethylcellulose ( EHEC ) , hydroxybutylmeth 37 , Polyquaternium - 44 , Polyquaternium - 46 , Polyquater ylcellulose (HBMC ) , hydroxyethylmethylcellulose nium -47 , Polyquaternium - 52 , Polyquaternium -53 , Poly (HEMC ) , hydroxypropylmethylcellulose (HPMC ), methyl quarternium -55 , Polyquaternium -59 , Polyquaternium -61 , cellulose (MC ) , hydroxyethylcellulose (HEC ) , hydroxypro Polyquaternium -64 , Polyquaternium -65 , Polyquaternium pylcellulose (HPC ) and cetyl hydroxyethylcellulose ) ; and 67 , Polyquaternium -69 , Polyquaternium - 70 , Polyquater mixtures thereof methylcellulose , polyethylene glycols ( e . g . , nium -71 , Polyquaternium -72 , Polyquaternium - 73 , Poly PEG 4000 , PEG 6000 , PEG 8000 , PEG 10000 , PEG 20000 ) , quaternium - 74 , Polyquaternium -76 , Polyquaternium - 77 , polyvinyl alcohol, polyacrylamides (homopolymers and Polyquaternium - 78 , Polyquaternium - 79 , Polyquaternium copolymers ) , and hydrophobically modified ethoxylated 80 , Polyquaternium - 81, Polyquaternium -82 , Polyquater urethanes (HEUR ) . The rheology modifier can be utilized in nium - 84 , Polyquaternium - 85 , Polyquaternium -87 , and an amount ranging from about 0 . 5 to about 25 wt. % in one PEG - 2 - cocomonium chloride . aspect, from about 1 to about 15 wt. % in another aspect , and [ 0243 ] Exemplary cationically modified natural polymers from about 2 to about 10 wt. % in a further aspect , based on suitable for use in the hair straightening composition include the weight of the total weight of the composition . polysaccharide polymers, such as cationically modified cel lulose and cationically modified starch derivatives modified Humectants with a quaternary ammonium halide moiety . Exemplary [0247 ] Humectants are defined as materials that absorb or cationically modified cellulose polymers are salts of release water vapor, depending on the relative humidity of hydroxyethyl cellulose reacted with trimethyl ammonium the environment, (Harry ' s Cosmeticology , Chemical Pub substituted epoxide (CTFA , Polyquaternium - 10 ) . Other suit lishing Company Inc ., 1982 p . 266 ) . Suitable humectants able types of cationically modified cellulose include the that include , but are not limited to , allantoin ; pyrrolidon polymeric quaternary ammonium salts of hydroxyethyl cel ecarboxylic acid and its salts ; hyaluronic acid and salts lulose reacted with lauryl dimethyl ammonium substituted thereof; sorbic acid and salts thereof; urea , lysine , cystine , epoxide (CTFA , Polyquaternium - 24 ) . Cationically modified and amino acids; polyhydroxy alcohols such as glycerin , US 2017 /0367963 A1 Dec . 28 , 2017 propylene glycol, hexylene glycol, hexanetriol, ethoxydigly - ( 0251 ] In one aspect , the hair care composition can con col , dimethicone copolyol, and sorbitol, and the esters tain from about 0 . 01 wt. % to about 10 wt . % of one or more thereof; polyethylene glycol; glycolic acid and glycolate of the botanical extracts set forth above , from about 0 .05 wt. salts ( e . g . ammonium and quaternary alkyl ammonium ) ; % to about to about 5 wt. % in another aspect, from about chitosan ; aloe - vera extracts ; algae extract ; honey and deriva 0 .1 wt. % to about 3 wt. % in still another aspect , and from tives thereof ; inositol; lactic acid and lactate salts ( e . g . about 0 . 5 wt. % to about 1 wt. % in a further aspect, based ammonium and quaternary alkyl ammonium ) ; sugars and on the total weight of the composition . Amino Acids starches ( e . g . , maltose , glucose , fructose ) ; sugar and starch [0252 ] The hair care composition provided herein can derivatives ( e . g ., glucose alkoxylated glucose , mannitol, contain one or more non - guanidine moiety containing amino xyliyol) ; DL - panthenol; magnesium ascorbyl phosphate , acids . Examples of amino acids that can be used include , arbutin , kojic acid , lactamide monoethanolamine ; acetamide without limitation , capryl keratin amino acids, capryl silk monoethanolamine ; and the like , and mixtures thereof . amino acids, jojoba amino acids , keratin amino acids, palmi Humectants also include the Cz to Co diols and triols , such toyl keratin amino acids, palmitoyl silk amino acids , sodium as glycerin , propylene glycol, butane - 1 , 2 , 3 - triol, hexylene cocoyl amino acids, sodium cocoyl silk amino acids , and glycol, hexanetriol, and the like , and mixtures thereof. sweet almond amino acids. Ethoxylated methyl glucose ethers containing an average of [0253 ] The hair straightening composition can include an 5 to 30 moles of ethoxylation , such as , for example , those appropriate amount of amino acid ( s ) . The amount of amino available under the INCI names Lauryl Methyl Gluceth - 10 acid ranges from about 0 .001 wt. % to about 5 wt. % in one Hydroxypropyldimonium chloride , Methyl Gluceth - 10 and aspect, from about 0 .01 wt. % percent to about 3 wt. % in Methyl Gluceth -20 , are suitable . another aspect , from about 0 .1 wt. % to about 2 wt. % in still [ 0248 ] Such humectants may be present at from 0 .01 - 20 another aspect, and from about 0 . 5 wt. % to about 1 wt. % wt. % of the composition , such as at least 0 . 1 wt. % , or at in a further aspect, based on the total weight of the compo least 1 wt. % , e . g . , up to 8 wt. % , or up to 5 wt. % . sition . Sensates Vitamins [ 0249 ] A skin sensate helps provide a sensory confirma tion of the adequacy , activity and evenness of the application 102541. The hair care composition can contain one or more thereof by a user. Some non - limiting examples of skin vitamins . Examples of vitamins that can be used include , sensates are described in U . S . Pat . Nos. 4 ,230 ,688 , 4 , 136 , without limitation , niacinamide , sodium starch octenylsuc 163 , 6 , 183, 766 and 7 , 001, 594 each of which are incorpo cinate , calcium pantothenate , maltodextrin , sodium ascorbyl rated herein by reference in their entireties. Non -limiting phosphate , tocopheryl acetate , pyridoxine HCl, silica , pan examples of suitable sensates include butanedioic acid thenol (e . g. , Pro Vitamin B5 ), phytantriol, calcium pantoth monomenthyl ester , camphor, carvone , cineole , clove oil , enate ( e . g . , vitamin B5 ) , vitamin E , and vitamin E esters ethyl carboxamide , ethyl menthane carboxamide, eucalyptus ( e. g ., tocopheryl acetate , tocopheryl nocotinate , tocopheryl oil , eucolytol, ginger oil, l -isopulegol , menthol, menthone palmitate , or tocopheryl retinoate ) . glycerin acetal, menthoxy - 1 , 2 - propanediol, menthyl lactate , [0255 ] A hair care composition provided herein can methyl diisopropylpropioniamide , methyl salicylate , pep include any amount of vitamin ( s ) . The amount of vitamin ( s ) permint oil, rosemary oil , trimethyl butanamide, vanillyl can range from about 0 .05 wt. % to about 10 wt. % in one butyl ether or combinations thereof. The sensate can be aspect, from about 0 . 1 wt . % to about 5 wt. % in another included in the composition in amounts ranging from about aspect, from about 0 .5 wt. % to about 3 wt. % in still another 0 .01 wt. % to about 2 wt. % in one aspect , and from about aspect , and from about 0 .75 wt. % to about 1 wt. % in a 0 .05 wt. % to about 1 wt. % in another aspect , based on the further aspect, based on the total weight of the composition . total weight of the composition . Botanicals [ 0250 ] The hair care compositions of the disclosed tech Chelating Agents nology can contain one or more botanical agents . Suitable botanical agents can include , for example , extracts from [0256 ] Chelating agents can be employed to stabilize the Echinacea ( e . g . , sp . angustifolia , purpurea , pallida ) , yucca composition against the deleterious effects of metal ions . glauca , willow herb , basil leaves , Turkish oregano , carrot When utilized , suitable chelating agents include EDTA root, grapefruit , fennel seed , rosemary , tumeric , thyme, ( ethylene diamine tetraacetic acid ) and salts thereof such as blueberry , bell pepper , blackberry , spirulina, black currant disodium EDTA , citric acid and salts thereof, cyclodextrins , fruit, tea leaves, such as for , example , Chinese tea, black tea and the like , and mixtures thereof. ( e. g ., var . Flowery Orange Pekoe, Golden Flowery Orange [0257 ] Such suitable chelating agents can comprise 0 . 001 Pekoe, Fine Tippy Golden Flowery Orange Pekoe ) , green wt. % to 3 wt. % , such as 0 . 01 wt. % to 2 wt. % , or 0 .01 wt. tea ( e . g . , var. Japanese , Green Darjeeling ) , oolong tea, coffee % to 1 wt. % of the total weight of the hair straightening seed , dandelion root, date palm fruit, gingko leaf, green tea, composition . hawthorn berry , licorice , apricot kernel, sage , strawberry , sweet pea , tomato , sunflower seed extract, sandalwood Buffer Agents extract, grape seed , aloe leaf, vanilla fruit, comfrey , arnica , Centella asiatica , cornflower , horse chestnut, ivy , Macada 10258 ] Buffering agents can be used in the exemplary mia ternifolia seed , magnolia , oat, pansy, skullcap , seabuck compositions . Suitable buffering agents include alkali or thorn , white nettle , and witch hazel. Botanical extracts may alkali earth metal carbonates , phosphates, bicarbonates, cit also include, for example, chlorogenic acid , glutathione , rates, borates, acetates , acid anhydrides, succinates, and the glycrrhizin , neohesperidin , quercetin , rutin , morin , myrice like , such as sodium phosphate , sodium citrate , sodium tin , absinthe , and chamomile . acetate , sodium bicarbonate , and sodium carbonate . US 2017 /0367963 A1 Dec . 28 , 2017 27 pH Adjusting Agents Moreover, formulating at low pH enhances the efficacy of acid based preservatives, and affords a personal care product [ 0259 ] The pH of the composition can range from to 1 . 5 which maintains an acidic pH balance on the skin . Any acid to 9 . 5 in one aspect , at least 4 . 5 in a second aspect, at least based preservative that is useful in personal care products 5 . 5 a third aspect, at least 6 . 5 in a fourth aspect , at least 7 .0 can be used in the exemplary compositions. In one aspect the in a fifth aspect, at least 7 . 5 in a sixth aspect, at least 8 . 0 in acid preservative is a carboxylic acid compound represented a seventh aspect, at least 8 . 5 in an eighth aspect, at least 9 . 0 by the formula : R8°C ( O )OH , wherein R80 represents hydro in a ninth aspect, and at least 9 . 5 in a tenth aspect. gen , a saturated and unsaturated hydrocarbyl group contain [ 0260 ] When polyvalent metal salts of pyrithione in com ing 1 to 8 carbon atoms or Co to C1 aryl. In another aspect , bination with secondary zinc salts are employed in the R8° is selected from a hydrogen , a C , to C , alkyl group , a C2 antidandruff hair care compositions of the disclosed tech to C , alkenyl group , or phenyl. Exemplary acids are , but are nology , the pH of the composition is adjusted to a value of not limited to , formic acid , acetic acid , propionic acid , sorbic at least about 6 . 5 . The pH can range from about 6 . 5 to about acid , caprylic acid , and benzoic acid , and mixtures thereof. 12 in one aspect, from about 6 . 8 to about 9 . 5 in another [0266 ] In another aspect , suitable acids include but are not aspect, and from about 6 . 8 to about 8 . 5 in still another limited to , oxalic acid , succinic acid , glutaric acid , adipic aspect . To provide the desired pH , the composition may be acid , azelaic acid , maleic acid , fumaric acid , lactic acid , adjusted with one or more pH modifiers selected from glyceric acid , tartronic acid malic acid , tartaric acid , glu organic and inorganic acids and bases . conic acid , citric acid , ascorbic acid , salicylic acid , phthalic [ 0261] The pH of the composition can be adjusted with acid , mandelic acid , benzilic acid , and mixtures thereof. any combination of acidic and /or basic pH adjusting agents ( 0267 ) Salts of the foregoing acids are also useful as long known to the art. Acidic materials include organic acids and as they retain efficacy at low pH values. Suitable salts inorganic acids, in particular, monocarboxylic acids , dicar include the alkali metal ( e . g . , sodium , potassium , calcium ) boxylic acids, and tricarboxylic acids, for example , acetic and ammonium salts of the acids enumerated above . acid , citric acid , tartaric acid , alpha -hydroxy acids, beta [0268 ]. The acid based preservatives and /or their salts can hydroxy acids , salicylic acid , lactic acid , malic acid , glycolic be used alone or in combination with non - acidic preserva acid , amino acids , and natural fruit acids, or inorganic acids, tives typically employed in personal care, home care , health for example , hydrochloric acid , nitric acid , sulfuric acid , care , and institutional and industrial care products . sulfamic acid , phosphoric acid , and combinations thereof. [0269 ] The preservatives may comprise from 0 .01 wt. % 10262] Basic materials include inorganic and organic to 3 . 0 wt. % in one aspect , or from about 0 . 1 wt. % to about bases , and combinations thereof. Examples of inorganic 1 wt. % , or from about 0 .3 wt. % to about 1 wt. % , of the bases include but are not limited to the alkali metal hydrox ides ( e . g . , potassium hydroxide , sodium hydroxide ) and total weight of the hair care composition . alkali metal carbonates ( e . g . , potassium carbonate , sodium Perfumes and Fragrances carbonate ) , and alkali metal salts such as sodium borate (borax ), sodium phosphate , sodium pyrophosphate , and the [0270 ] Fragrance and perfume components that may be like; and mixtures thereof. Examples of organic bases used in the exemplary composition to mask the odor of any include ammonium hydroxide, triethanolamine ( TEA ), of the various components in the hair straightening compo diisopropanolamine , triisopropanolamine , aminomethyl sition or to give the composition an aesthetically pleasing propanol, dodecylamine, cocamine , oleamine , morpholine , fragrance . In one aspect , suitable fragrances and perfumes triamylamine , triethylamine, tetrakis (hydroxypropyl ) ethyl include natural and synthetic fragrances , perfumes , scents , enediamine , L - arginine , aminomethyl propanol, trometh and essences and any other substances which emit a fra amine ( 2 - amino 2 -hydroxymethyl - 1 , 3 - propanediol ), and grance . As the natural fragrances, there are those of veg PEG - 15 cocamine . etable origin , such as oil extracts from flowers ( e. g . , lily , lavender , rose , jasmine , neroli, ylang -ylang ) , stems and [ 0263] The pH adjusting agent( s) and /or buffering agent is leaves ( geranium , patchouli, petitgrain , peppermint ) , fruits utilized in any amount necessary to obtain and / or maintain ( aniseed , coriander , fennel, mace , needle juniper) , fruit skin a desired pH value in the composition . (bergamot , lemon , orange ) , roots ( angelica , celery , carda mom , costus , iris , sweet flag ) , woods (pine tree , sandalwood , Preservatives guaiacum wood , cedar, rosewood , cinnamon ), herbs and [ 0264 ] In one aspect, any preservative suitable for use in grasses ( tarragon , lemongrass, sage , thyme ) , needles and personal care can be used in the composition for straight twigs (spruce , pine , European red pine, stone pine ), and ening hair . Suitable preservatives include polymethoxy bicy resins and balsam ( galbanum , elemi, benzoin , myrrh , frank clic oxazolidine , methyl paraben , propyl paraben , ethyl incense , opopanax ) , and those of animal origin , such as paraben , butyl paraben , benzyltriazole , DMDM hydantoin musk , civet , castoreum , ambergris , or the like , and mixtures ( also known as 1 , 3 - dimethyl- 5 , 5 - dimethyl hydantoin ) , imi thereof . dazolidinyl urea , phenoxyethanol, phenoxyethylparaben , [0271 ] Examples of synthetic fragrances and perfumes are methylisothiazolinone , methylchloroisothiazolinone, benzo the aromatic esters , ethers , aldehydes, ketones , alcohols , and isothiazolinone, triclosan , and suitable polyquaternium com hydrocarbons including benzyl acetate , phenoxyethyl isobu pounds as disclosed above ( e . g ., Polyquaternium - 1 ) . tylate , p -tert - butylcyclohexyl acetate , linalyl acetate , dim [ 0265 ] In another aspect , acid based preservatives are ethylbenzylcarbinyl acetate , phenylethyl acetate , linaly1 useful in the exemplary compositions. The use of acid based benzoate , benzyl formate , ethylmethylphenyl glycinate , preservatives facilitates the formulation of products in the allylcyclohexyl propionate , styralyl propionate , and benzyl low pH range. Lowering the pH of a formulation inherently salicylate ; benzylethyl ether; straight chain alkanals having provides an inhospitable environment for microbial growth 8 to 18 carbon atoms, citral, citronellal , citronellyloxyalde in addition to being suited to the straightening process . hyde, cyclamen aldehyde , hydroxycitronellal, lilial, and US 2017 /0367963 A1 Dec . 28 , 2017 28 bougeonal; ionone compounds , a - isomethyl ionone, and particles, barium oxide , ultramarine blue, bismuth citrate , methyl cedryl ketone ; anethole , citronellol, eugenol, hydroxyapatite, zirconium silicate , carbon black particles, isoeugenol, geraniol, lavandulol, nerolidol, linalool, pheny and the like . lethyl alcohol , and terpineol, alpha -pinene , terpenes ( e. g. , limonene ), and balsams, and mixtures thereof. Detersive Compositions [ 0272] The amount of fragrance agent or perfume [ 0277 ] Surprisingly , the nonionic , amphiphilic emulsion employed can be any amount suitable to mask a particular polymers of the disclosed technology can be activated by a odor or to impart a desired aesthetically pleasing aroma, surfactant to provide a stable yield stress hair care compo fragrance or scent. In one aspect, the amount of fragrance sition with desirable rheological and aesthetic properties and agent can range from about 0 .05 wt. % to about 10 wt. % , the ability to suspend particulate and insoluble materials in from about 0 . 1 wt. % to about 5 wt. % in another aspect, an aqueous medium for indefinite periods of time indepen from about 0 . 5 wt. % to about 3 . 5 wt. % in still another dent of pH . The yield stress value , elastic modulus and aspect, and from about 1 wt. % to about 2 . 5 wt. % in a optical clarity are substantially independent of pH in the further aspect , based on the total weight of the composition . compositions in which the present polymers are included . The nonionic , amphiphilic emulsion polymers of the dis Electrolytes closed technology are useful in the pH range of from about 2 to about 14 in one aspect, from about 3 to 11 in another [0273 ] Optionally , the cleansing and conditioning compo aspect, and from about 4 to about 9 in a further aspect . sitions of the disclosed technology can contain an electro Unlike the pH responsive crosslinked polymers (acid or base lyte . Suitable electrolytes are known compounds and include sensitive ) that require neutralization with an acid or a base salts of multivalent anions, such as potassium pyrophos to impart a desired rheological profile , the crosslinked , phate , potassium tripolyphosphate , and sodium or potassium nonionic , amphiphilic emulsion polymers of the disclosed citrate , salts of multivalent cations, including alkaline earth technology are substantially independent of pH . By substan metal salts such as calcium chloride and calcium bromide , as tially independent of pH is meant that the yield stress fluid well as zinc halides , barium chloride , magnesium sulfate and within which the polymer of the disclosed technology is calcium nitrate , salts of monovalent cations with monova included imparts a desired rheological profile ( e . g . , a yield lent anions, including alkali metal or ammonium halides , stress of at least 0 . 1 Pa in one aspect, at least at least 0 . 5 Pa such as potassium chloride , sodium chloride , potassium in another aspect, at least 1 Pa in still another aspect, and at iodide , sodium bromide , and ammonium bromide , alkali least 2 Pa in a further aspect) across a wide pH range ( e . g ., metal or ammonium nitrates , and blends thereof. The from about 2 to about 14 ) wherein the standard deviation in amount of the electrolyte used will generally depend on the yield stress values across the pH range is less than 1 Pa in amount of the amphiphilic emulsion polymer incorporated , one aspect, less than 0 .5 Pa in another aspect, and less than butmay be used at concentration levels of from about 0 . 1 to 0 . 25 Pa in a further aspect of the . about 4 wt. % in one aspect and from about 0 . 2 to about 2 [0278 ] In one exemplary aspect, the hair care composi wt. % in another aspect, based on the weight of the total tions comprise : i ) at least one nonionic , amphiphilic emul composition . sion polymer; ii ) at least one surfactant selected from at least one anionic surfactant, at least one amphoteric surfactant, at Dyes and Pigments least one nonionic surfactant, and combinations thereof ; iii ) at least one particulate antidandruff agent; and iv ) water. [ 0274 ] The hair care compositions of the present technol 02791. In another exemplary aspect, the hair care compo ogy may also contain pigment materials such as inorganic , sitions comprise : i ) at least one crosslinked , nonionic , nitroso , monoazo , disazo , carotenoid , triphenyl methane , amphiphilic emulsion polymer ; ii ) at least one anionic triaryl methane, xanthene , quinoline , oxazine , azine , anthra surfactant; iii ) at least one particulate antidandruff agent; and quinone , indigoid , thionindigoid , quinacridone , phthalocia iv ) water. nine, botanical , natural colors , including: water soluble [ 0280 ] In another exemplary aspect , the hair care compo components such as those having C . I . and FD & C designa sitions comprise : i ) at least one crosslinked , nonionic , tions. amphiphilic emulsion polymer; ii ) at least one anionic [ 0275 ] Exemplary pigments are metal compounds or semi surfactant and at least one amphoteric surfactant; iii ) at least metallic compounds and may be used in ionic , nonionic or one particulate antidandruff agent; and iv ) water . oxidized form . The pigments can be in this form either [0281 ] In another exemplary aspect, the hair care compo individually or in admixture or as individual mixed oxides or sitions comprise : i ) at least one crosslinked , nonionic , mixtures thereof, including mixtures of mixed oxides and amphiphilic emulsion polymer ; ii ) at least one anionic pure oxides . Examples are the titanium oxides ( e . g ., TiO2) , surfactant, iii ) an optional nonionic surfactant; iv ) a particu zinc oxides ( e . g ., ZnO ) , aluminum oxides ( for example , late antidandruff agent; and v ) water. Al2O3 ), iron oxides ( for example , Fe2O3 ), manganese oxides [0282 ] In another exemplary aspect , the hair care compo ( e . g . , MnO ), silicon oxides ( e . g . , SiO2) , silicates, cerium sitions comprise : i ) at least one crosslinked , nonionic , oxides, zirconium oxides ( e . g ., Zro , ), barium sulfate amphiphilic emulsion polymer ; ii ) at least one anionic (BaSO4 ) , nylon - 12 , and mixtures thereof. surfactant, iii ) an amphoteric surfactant; iv ) an optional [ 0276 ] Other examples of pigments include thermochro nonionic surfactant; v ) a particulate antidandruff agent; and mic dyes that change color with temperature , calcium car vi ) water . bonate , aluminum hydroxide, calcium sulfate , kaolin , ferric [0283 ] In another exemplary aspect , the hair care compo ammonium ferrocyanide, magnesium carbonate , carmine , sitions comprise : i ) at least one crosslinked , nonionic , barium sulfate , mica , bismuth oxychloride , zinc stearate , amphiphilic emulsion polymer; ii) at least one anionic manganese violet, chromium oxide, titanium dioxide nano ethoxylated surfactant; iii ) an optional nonionic surfactant ; US 2017 /0367963 A1 Dec . 28 , 2017 iv ) a particulate antidandruff agent; and v ) water. In one about 0 . 5 to about 5 wt. % polymer solids ( 100 % active aspect , the average degree of ethoxylation in the anionic polymer ) based on the weight of the total composition . In ethoxylated surfactant can range from about 1 to about 3 . In another aspect, the amount of polymer utilized in the for another aspect , the average degree of ethoxylation is about mulation ranges from about 0 .75 wt. % to about 3 . 5 wt. % . 2 . In still another aspect , the amount of amphiphilic emulsion [ 0284 ] In another exemplary aspect, the hair care compo polymer employed in the hair care composition ranges from sitions comprise : i ) at least one crosslinked , nonionic , about 1 to about 3 wt. % . In a further aspect, the amount of amphiphilic emulsion polymer ; ii ) at least one anionic polymer employed in the hair care composition ranges from ethoxylated surfactant; iii ) at least one amphoteric surfac about 1 . 5 wt. % to about 2 .75 wt. % . In a still further aspect, tant; iv ) at least one particulate antidandruff agent; v ) an the amount of polymer utilized in the hair care composition optional nonionic surfactant; and vi ) water. In one aspect, ranges from about 2 to about 2 . 5 wt . % , all weights based on the average degree of ethoxylation in the anionic ethoxy the weight of the total composition . lated surfactant can range from about 1 to about 3 . In another [0291 ] The hair care compositions of the disclosed tech aspect, the average degree of ethoxylation is about 2 . nology may be in the form of a shampoo , two - in -one [0285 ] In another exemplary aspect, the hair care compo shampoo , conditioner, creme rinse, body wash , shower gel, sitions comprise : i ) at least one crosslinked , nonionic , and the like . amphiphilic emulsion polymer; ii) at least one anionic [0292 ] In one embodiment, the hair care composition of non - ethoxylated surfactant; iii ) at least one anionic ethoxy the disclosed technology is a moderately viscous mixture , lated surfactant; iv ) an optional nonionic surfactant ; v ) at having a Brookfield viscosity in the range of from about least one particulate antidandruff agent; and vi) water. In one 1000 mPa. s to about 15 ,000 mPa. s in one aspect , from about aspect, the average degree of ethoxylation in the anionic 2 ,000 mPa . s to about 10 , 000 mPa . s in another aspect , from ethoxylated surfactant can range from about 1 to about 3 . In about 3 , 500 mPa .s to about 8 , 500 mPa . s in still another another aspect, the average degree of ethoxylation is about aspect, and from about 4 ,500 mPa . s to about 5500 mPa . s in a further aspect. The viscosities are adjustable by changing [ 0286 ] In another exemplary aspect, the hair care compo the amount of nonionic , amphiphilic emulsion polymeric sitions comprise : i ) at least one crosslinked , nonionic , material in the hair care composition . The product should be amphiphilic emulsion polymer ; ii ) at least one anionic pourable from a relatively narrow mouth bottle ( approxi non -ethoxylated surfactant; iii ) at least one anionic ethoxy mately 1 .5 cm in diameter ) and the product will not be so lated surfactant; iv ) at least one amphoteric surfactant; v ) an thin to run off of the hands or the hair . optional nonionic surfactant ; vi ) at least one particulate [0293 ] Hair care compositions of the present technology antidandruff agent; and vi ) water. In one aspect, the average are stable indefinitely at temperatures normally found in degree of ethoxylation in the anionic ethoxylated surfactant commercial product storage and shipping . The compositions can range from about 1 to about 3 . In another aspect, the resist phase separation or settling of composition ingredients average degree of ethoxylation is about 2 . at a temperature of about 20° C . to about 25° C . essentially [ 0287 ] In another exemplary aspect, the hair care compo indefinitely . The compositions also must demonstrate suffi sitions comprise : i) at least one crosslinked , nonionic , cient stability to phase separation and settling of ingredients amphiphilic emulsion polymer ; ii ) at least one anionic at temperatures normally found in commercial product stor non - ethoxylated surfactant; iii ) at least one anionic ethoxy age and shipping to remain unaffected for periods of one lated surfactant; iv ) at least one amphoteric surfactant; v ) an year or more . optional nonionic surfactant; vi ) zinc pyrithione antidandruff [ 0294 ] Hair care cleansing compositions employing the agent ; and vi) water. In one aspect , the average degree of nonionic , amphiphilic emulsion polymers of the disclosed ethoxylation in the anionic ethoxylated surfactant can range technology not only provide compositions in which they are from about 1 to about 3 . In another aspect , the average contained with enhanced suspension stability , they also degree of ethoxylation is about 2 . provide other unexpected desirable properties such as foam [ 0288 ] In another exemplary aspect , the hair care compo quality , irritation mitigation , and enhanced silicone deposi sitions comprise : i ) at least one crosslinked , nonionic , tion . amphiphilic emulsion polymer ; ii) at least one anionic [0295 ] The hair care compositions of the disclosed tech non - ethoxylated surfactant ; iii ) at least one anionic ethoxy nology may be prepared by any known technique. The lated surfactant ; iv ) at least one amphoteric surfactant; v ) an formulation of hair care antidandruff cleansing compositions optional nonionic surfactant; vi ) zinc pyrithione antidandruff are well -known in the formulation art and include conven agent; vi) basic zinc carbonate ; and vii ) water. In one aspect, tional formulation and mixing techniques. In one embodi the average degree of ethoxylation in the anionic ethoxy ment, the nonionic , amphiphilic emulsion polymers of the lated surfactant can range from about 1 to about 3 . In another disclosed technology can be added to any commercially aspect , the average degree of ethoxylation is about 2 . available antidandruff hair care composition to enhance the [ 0289] Any amount of the nonionic , amphiphilic emulsion suspension stability thereof. Given the pH independent polymeric material can be utilized so long as the amount is nature of the nonionic , amphiphilic emulsion polymer dis sufficient to suspend an insoluble material ( e . g ., antidandruff closed herein , it can be added at any point during the agent, silicone , etc . ) when included in an aqueous hair care commercial production process of antidandruff hair care composition comprising at least one surfactant selected from cleansing products . anionic surfactants , amphoteric surfactants , nonionic surfac [0296 ] The compositions of the present technology can be tants , and combinations thereof. used in direct application to the hair , scalp and skin in a [0290 ] In one aspect, the amount of the polymer that can conventional manner for cleansing skin and hair and con be incorporated into the aqueous surfactant containing hair trolling dandruff on the skin or scalp . The compositions care compositions of the disclosed technology ranges from herein are useful for cleansing the hair and scalp , and other US 2017 /0367963 A1 Dec . 28 , 2017 30 areas of the body such as underarm , feet, and groin areas and -continued for any other area of skin in need of treatment. The present technology may be used for treating or cleansing of the skin Spindle Size No . Viscosity Range (mPa · s ) or hair of animals as well . An effective amount of the 1 , 000 - 5 , 000 composition for application , typically ranges from about 1 g ??? 5 , 000 - 10 , 000 to about 50 g in one aspect, and from about 1 g to about 20 10 ,000 - 20 ,000 g in another aspect, for cleansing hair , skin or other area of ??? 20 ,000 - 50 , 000 the body . The composition is topically applied to the hair , > 50 ,000 skin or other area that has preferably been wetted , generally with water , and then rinsed off . Application to the hair [0301 ] The spindle size recommendations are for illustra typically includes working the cleansing composition tive purposes only. The artisan of ordinary skill in the art will through the hair with the fingers to build up lather . select a spindle size appropriate for the system to be mea [ 0297] In one embodiment , one method for providing sured . antidandruff efficacy with a shampoo embodiment com prises the steps of: (a ) wetting the hair with water , (b ) Stability applying an effective amount of the antidandruff shampoo [0302 ] The various hair care products or compositions composition to the hair, and (c ) rinsing the antidandruff made using the nonionic , amphiphilic emulsion polymers shampoo composition from the hair using water . These steps rheology of the present technology are stable . The stability may be repeated as many times as desired to achieve the requirements for a particular composition will vary with its cleansing , conditioning , and anti -dandruff benefits sought. end marketplace application as well as the geography in [ 0298 ] This technology is illustrated by the following which it is to be bought and sold . An acceptable " shelf life " examples that are merely for the purpose of illustration and is subsequently determined for each composition . This are not to be regarded as limiting the scope of the technology refers to the amount of time that a composition should be or the manner in which it can be practiced . Unless specifi stable across its normal storage and handling conditions , cally indicated otherwise , parts and percentages are given by measured between the times that the composition is pro weight. duced and when it is finally sold for consumer use . Gener ally , Personal Care compositions require a 1 to 3 year shelf Test Methods life . 0303 ] To eliminate the need to conduct stability studies in Yield Stress excess of one year, the formulator will conduct stability [ 0299] The yield stress values of these polymers are testing at stressed conditions in order to predict the shelf life determined by oscillatory and steady shearmeasurements on of a composition . Typically , accelerated testing is conducted a controlled stress rheometer ( TA Instruments AR1000N at elevated static temperatures, usually 45 -50° C . A compo rheometer , New Castle , Del. ) utilizing parallel plate geom sition should be stable for at least 2 weeks, desirably 1 etry (40 mm stainless steel plate with a 1000 um gap ) at 25° month , preferably 2 or 3 months, and most preferably 4 or C . The oscillatory measurements are performed at a fixed 5 months at 45° C . Additionally , freeze - thaw cycling is often frequency of 1 rad / sec . The elastic and viscous moduli ( G ' employed wherein the composition is cycled between a and G " respectively ) are obtained as a function of increasing freezing temperature , usually 0° C . , and an ambient tem stress amplitude . In cases where the swollen polymer par perature , usually 20 - 25° C . A composition should pass a ticles create a network , G ' is larger than G " at low stress minimum of 1 freeze - thaw cycle , preferably 3 cycles, and amplitudes but decreases at higher amplitudes crossing G " most preferably 5 cycles. because of rupture of the network . As illustrated in FIG . 1 [0304 ] Products or compositions made according to the the stress corresponding to the crossover of G ' and G " is present technology are considered stable if they meet one or more of the following criteria : noted as the yield stress. 1 . There is no phase separation , settling , or creaming of any material in the composition . The composition should remain Viscosity (Brookfield ) completely homogenous throughout its bulk . Separation is [ 0300 ] Brookfield rotating spindle method (all viscosity herein defined as the visible existence of 2 or more distinct measurements reported herein are conducted by the Brook layers or phases of any component in the formulation , field method whether mentioned or not) : The viscosity including but not limited to insoluble matter, soluble matter , measurements are calculated in mPa . s , employing a Brook oily substances and the like . field rotating spindle viscometer, Model RVT (Brookfield 2 . The viscosity of the composition does not significantly Engineering Laboratories , Inc . ) , at about 20 revolutions per increase or decrease over time, generally less than 50 % , minute ( rpm ), at ambient room temperature of about 20 to preferably less than 35 % , and most preferably less than 25° C . (hereafter referred to as viscosity ) . Spindle sizes are 20 % . selected in accordance with the standard operating recom 3 . The pH of the composition does not increase or decrease mendations from the manufacturer. Generally , spindle sizes more than two pH units , preferably not more than one unit , are selected as follows: and most preferably not more than one - half unit . 4 . The rheology and texture of the composition does not significantly change over time to that which is unacceptable . Spindle Size No. Viscosity Range (mPa · s ) [0305 ] Products or compositions made according to the 1 - 50 present technology are considered unstable if they do not NE 500 - 1 , 000 meet one or more of the above listed criteria . Further information on stability testing requirements can be found in US 2017 /0367963 A1 Dec . 28 , 2017 31

“ The Fundamentals of Stability Testing ; IFSCC Monograph Abbreviations and Trade Names Number 2 ” , published on behalf of the International Fed eration of Societies of Cosmetic Chemists by Micelle Press , [0311 ] Weymouth , Dorset, England , and Cranford , N . J . , U . S . A . and is herein incorporated by reference . AMD Acrylamide AMPS ® Monomer 2 -Acrylamido - 2 -Methylpropanesulfonic Acid , Lubrizol Advanced Materials , Inc . Hair Tress Preparation Procedure for Silicone Deposition AN Acrylonitrile Testing APE Allyl Pentaerythritol n - BA n - Butyl Acrylate [ 0306 ] Tresses of commercially blended untreated (virgin ) BDGMA Butyl Diglycol Methacrylate BEM Sipomer ® Ethoxylated (25 ) Behenyl human hair are prepared employing natural brown or black Methacrylate , Rhodia color European hair supplied by International Hair Importers i - BMA iso - Butyl Methacrylate and Products Inc . , New York . The tresses used for this test S - BMA sec - Butyl Methacrylate are comprised of European brown hair , weighing 0 . 5 g , 7 ChembetaineTM CAD Cocamidopropyl Betaine ( amphoteric inches long and 0 . 5 inches wide with a sewn / glued flat surfactant ) , Lubrizol Advanced Materials , Inc . ( 35 % active ) binding . Prior to treatment, each tress is washed with a dilute CSEM Visiomer ® C18 PEG 1105 MA W aqueous solution of sodium lauryl sulfate ( 10 % SLS ) fol Polyethyleneglycol (25 ) Cetearyl Methacrylate , lowed by thorough rinsing with de - ionized water at ambient Evonik Röhm GmbH CYCLO Cyclohexane room temperature . The tresses are dried by towel blotting . Celvol ® 502 PVA Polyvinyl Alcohol (hydrolysis % = 87 - 89 % ) , [ 0307 ] The damp tress is placed on top of a weighing dish Celanese Corpoartion EA Ethyl Acrylate and 0 . 25 g of the test shampoo formulation is applied evenly EMA Ethyl Methacrylate down the length of the tress . The shampoo is massaged into E - Sperse RS - 1596 Reactive surfactant with one polymerizable the swatch and the tress is then rinsed under warm tap water reactive group from Ethox Chemical, LLC for approximately 60 seconds. The treatment step is repeated E - Sperse RS- 1616 Reactive surfactant with one polymerizable reactive group from Ethox Chemical, LLC a second time for a total of two wash /rinse cycles . E -Sperse RS - 1617 Amphiphilic crosslinker with two polymerizable reactive groups from Ethox Chemical , LLC E -Sperse RS - 1618 Amphiphilic crosslinker with two polymerizable Silicone Deposition Measurement reactive groups from Ethox Chemical, LLC E -Sperse RS - 1684 Amphiphilic crosslinker with two polymerizable [ 0308 ] The amount of silicone ( silicon atoms) deposited reactive groups from Ethox Chemical , LLC on the hair tress samples treated with a test shampoo 2 -HEA 2 -Hydroxyethyl Acrylate HEMA 2 -Hydroxyethyl Methacrylate composition containing the nonionic , amphiphilic emulsion ??? Hydroxypropyl Acrylate polymer is measured by X -Ray fluorescence (XRF ) spec ???? 3 -Hydroxypropyl Methacrylate troscopy . A wavelength dispersive XRF spectrometer LEM Blemmer ® PLE - 200 Lauroxy Polyethyleneglycol Methacrylate , NOF (PANalytical Axios Advanced Sequential 4 kW spectrom Corporation eter — Model Number PW4400 ) interfaced with SuperQ 4 LMA Lauryl Methacrylate software application and fitted with a rhodium tube with an MA Methyl Acrylate InSb crystal is utilized to facilitate high sensitivity for MAA Methacrylic Acid MA EO /PO -300 Blemmer ® 50PEP -300 Polyethyleneglycol silicon atom detection corresponding to Si K alpha band . ( 3 . 5 ) Polypropyleneglycol ( 2 . 5 ) Methacrylate , The samples are analyzed using a qualitative program to NOF Corporation measure intensities across a two -theta scan range from MA EO /PO - 800 , Blemmer ® 55PET - 800 Polyethyleneglycol 139. 750 to 147 . 990 with a peak maximum at 144 . 53° . The ( 10 ) Polypropyleneglycol ( 5 ) Methacrylate , samples are scanned in a vacuum environment using a tube NOF Corporation MAMD Methacrylamide voltage of 25 kV and a current of 160 mA. Scanning speed MMA Methyl Methacrylate is 0 . 05° 2 - Theta /sec . with 0 .02° 2 - Theta step size . MPEG 350 Bisomer ® 350 MA Methoxy Polyethyleneglycol ( 8 ) Methacrylate , GEO Specialty Chemicals [ 0309] X - rays from the instrument excite silicon atoms MPEG 400 Blemmer ® PME -400 Methoxy deposited on the surface of the wool swatch causing them to Polyethyleneglycol (9 ) Methacrylate , NOF emit energy and fluoresce . The silicon fluorescence is Corporation MPEG S10 W Bisomer ® S10 W Methoxy Polyethyleneglycol detected and recorded as counts per second (kcps ). Higher ( 23 ) Methacrylate , GEO Specialty Chemicals count rates are indicative of higher silicon atom deposition . NPEA - 1300 Blemmer ® ANE - 1300 , Nonylphenoxy The amount of silicon atoms detected is directly propor Polyethyleneglycol (30 ) Acrylate , NOF tional to the amount of silicone conditioner deposited on the Corporation OEO / POMA Blemmer ® 50POEP - 800B Octoxy hair . Samples for XRF analysis are prepared by folding each Polyethyleneglycol ( 8 ) Polypropyleneglycol ( 6 ) of the treated wool swatches and placing the folded swatch Methacrylate , NOF Corporation (hydrophobe = into a sample cup having a bu thick polyethylene support 2 -ethylhexyl ) PEA Blemmer ® AAE - 300 Phenoxy substrate formed into the bottom . A polyethylene spacer is Polyethyleneglycol (5 .5 ) acrylate , NOF placed on each swatch to hold it onto the substrate . An Corporation average reading of 3 hair tresses per formulation is reported . PEO /POMA Blemmer ® 43PAPE - 600B Phenoxy Results are reported as average Peak Si Intensity (kcps ) . Polyethyleneglycol ( 6 ) Polypropyleneglycol (6 ) Higher kcps values indicate higher levels of silicon atom Methacrylate , NOF Corporation deposition . SEM - 400 Blemmer ® PSE -400 Stearoxy Polyethyleneglycol ( 9 ) Methacrylate , NOF [ 0310 ] The following abbreviations and trade names are Corporation utilized in the examples. US 2017 /0367963 A1 Dec . 28 , 2017 32

resulting emulsion was adjusted to 4 .5 with ammonium - continued hydroxide . The polymer product had a solids content of SEM - 1300 Blemmer ® PSE - 1300 Stearoxy Polyethyleneglycol ( 30 ) Methacrylate, NOF 30 . 4 % , a viscosity of 21 cps, and a particle size of 119 nm . Corporation SMA Stearyl Methacrylate Example 2 Selvol ® 502 and Polyvinyl Alcohol ( hydrolysis % = 87- 89 % ), 205 PVA Sekisui Corporation Monomer Composition = EA / n -BA / HEMA /BEM STYSEM - 25 Sipomer ® , w - Tristyrylphenyl Polyoxyethylene ( 25 ) Methacrylate ) ( 35 / 15 /45 / 5 ) Wt. Sulfochem TM ALS - K Ammonium Lauryl Sulfate (anionic surfactant [0313 ] An emulsion polymer was prepared as follows. A preserved with Kathon ® CG preservative from monomer premix was made by mixing 140 grams of DI Rohm and Haas Company ), Lubrizol Advanced Materials, Inc . ( 30 % active ) water, 5 grams of E -Sperse® RS - 1618 amphiphilic cross SulfochemTM ES - 2 Sodium Laureth Sulfate - 2 moles of linker, 175 grams of (EA ) , 75 grams of ( n - BA ), 225 grams ethoxylation (anionic surfactant) , Lubrizol of (HEMA ) and 33 . 3 grams of ( BEM ) . Initiator A was made Advanced Materials , Inc . ( 26 % active ) Sulfochem TM SLS Sodium Lauryl Sulfate (anionic surfactant ), by mixing 3 .57 grams of TBHP in 40 grams of DI water. Lubrizol Advanced Materials, Inc . ( 30 % active ) Reductant A was prepared by dissolving 0 . 13 grams of Sulfochem TM TLS TEA - Lauryl Sulfate ( anionic surfactant) Lubrizol erythorbic acid in 5 grams of DI water. Reductant B was Advanced Materials, Inc. (40 % active ) prepared by dissolving 2 . 5 grams of erythorbic acid in 100 TBHP tert- butyl t -butyl hydroperoxide grams of DI water . A 3 - liter reactor was charged with 825 VA Vinyl Acetate VA - 10 Vinyl Decanoate grams of DIwater , 7 . 5 grams of 40 % AOS and 15 grams of VP N - Vinylpyrrolidone Selvol® 502 PVA , and then the contents were heated to 70° i - PAMD iso - Propylacrylamide C . under a nitrogen blanket with agitation . After holding the MAMD Methacrylamide reactor contents at 70° C . for one hour, the contents of the reactor were cooled down to 65° C ., and then initiatorAwas then added to the reactor followed by addition of reductant Example 1 A . After about 1 minute , the monomer premix was metered into the reaction vessel over a period of 180 minutes . About 3 minutes after the start of monomer premix introduction , Monomer Composition = EA/ n - BA /HEMA / BEM reductant B was metered into the reactor over a period of ( 35 / 15 / 45 / 5 ) Wt. 210 minutes . After completion of the reductant B feed , the [ 0312 ] An emulsion polymer was prepared as follows . A temperature of the reaction vessel contents was maintained monomer premix was made by mixing 140 grams of DI at 65° C . for 60 minutes. The reactor contents were then water, 5 grams of E -Sperse® RS - 1618 amphiphilic cross cooled to 60° C . A solution of 1 . 96 grams of TBHP and 0 . 13 linker, 175 grams of ( EA ), 75 grams of ( n -BA ), 225 grams grams of 40 % AOS in 15 grams of DI water was added to of (HEMA ) and 33 . 3 grams of (BEM ). Initiator Awas made the reactor . After 5 minutes , a solution of 1 . 27 grams of by mixing 2 . 86 grams of TBHP in 40 grams of DI water . erythorbic acid in 15 grams of DI water was added to the Reductant A was prepared by dissolving 0 . 13 grams of reactor . The reactor contents were maintained at 60° C . After erythorbic acid in 5 grams of DI water. Reductant B was 30 minutes, a solution of 1 . 96 grams of TBHP and 0 . 13 prepared by dissolving 2 . 0 grams of erythorbic acid in 100 grams of 40 % AOS in 15 grams of DI water was added to grams of DI water. A 3 - liter reactor was charged with 800 the reactor. After 5 minutes, a solution of 1 . 27 grams of grams of DI water, 10 grams of 40 % AOS and 25 grams of erythorbic acid in 15 grams of DI water was added to the Selvol® 502 PVA . The contents of the reactor were heated reactor. The reactor contents were maintained at 60° C . for to 70° C . under a nitrogen blanket with agitation . After about 30 minutes . Then , the reactor contents were cooled to holding the reactor contents at 70° C . for one hour , initiator room temperature (22° C . ) and filtered through 100 micron Awas added to the reactor followed by addition of reductant filter cloth . The pH of the resulting emulsion was adjusted to A . After about 1 minute , the monomer premix was metered 4 . 5 with ammonium hydroxide . The polymer product had a into the reaction vessel over a period of 180 minutes. About solids contentof 30 .85 % , a viscosity of 19 cps, and a particle 3 minutes after the start of monomer premix introduction , size of 99 nm . reductant B was metered to the reactor over a period of 210 minutes . The reaction temperature was kept at 65° C . After Example 3 completion of reductant B feed , the temperature of the reaction vessel contents was maintained at 65° C . for 60 Monomer Composition = EA / n -BA /HEMA / BEM /APE minutes . The reactor contents were then cooled to 60° C . A (35 / 15 /45 / 5 ) Wt. solution of 1 .79 grams of TBHP and 0 . 13 grams of 40 % [0314 ] An emulsion polymer employing APE crosslinker AOS in 15 grams of DI water was added to the reactor. After was prepared as follows. A monomer premix was made by 5 minutes , a solution of 1 .05 grams of erythorbic acid in 15 mixing 140 grams of DI water, 5 grams of E - Sperse® grams of DI water was added to the reactor. The reactor RS - 1618 amphiphilic crosslinker, 175 grams of (EA ) , 70 .6 contents were maintained at 60° C . After 30 minutes , a grams of ( n -BA ), 225 grams of (HEMA ) and 33 .3 grams of solution of 1 .79 grams of TBHP and 0 . 13 grams of 40 % (BEM ) . Initiator A was made by mixing 3 . 57 grams of AOS in 15 grams of DIwater was added to the reactor. After TBHP in 40 grams of DI water . Reductant A was prepared 5 minutes , a solution of 1 . 05 grams of erythorbic acid in 15 by dissolving 0 . 13 grams of erythorbic acid in 5 gramsof DI grams of DI water was added to the reactor. The reactor water . Reductant B was prepared by dissolving 2 .5 grams of contents were maintained at 60° C . for about 30 minutes . erythorbic acid in 100 grams of DI water . A 3 - liter reactor Then , the reactor was cooled to room temperature and was charged with 800 grams of DI water, 10 grams of 40 % filtered through 100 micron filter cloth . The pH of the AOS and 25 grams of Selvol® 502 PVA and then was heated US 2017 /0367963 A1 Dec . 28 , 2017 33 to 70° C . under a nitrogen blanket with proper agitation . solution of 0 . 59 grams of erythorbic acid in 15 grams of DI After holding the reactor at 70° C . for one hour, initiator A water was added to the reactor. The reactor contents were was added to the reactor and followed by addition of maintained at 49° C . for about 30 minutes . The reactor was reductant A . After about 1 minute , themonomer premix was cooled to the room temperature and filtered through 100 metered to the reaction vessel over a period of 180 minutes . micron filter cloth . The pH of the resulting emulsion was About 3 minutes after the start of monomer premix intro adjusted to 4 . 5 with ammonium hydroxide . The polymer duction , reductant B was metered to the reactor over a period product had a solids content of 31. 4 % , a viscosity of 14 cps of 210 minutes . The reaction temperature was kept at 65° C . and a particle size of 105 nm . At about 115 minutes after the monomer premix introduc tion , the premix metering was stopped for 10 minutes , and Example 5 then 0 . 44 grams of 70 % APE in 3 . 94 grams of n - BA was added to the monomer premix . After the 10 minute period , Monomer Composition = EA / n -BA / HEMA / BEM the premix metering was resumed . After completion of ( 30 / 20 /45 / 5 ) Wt. reductant B feed , the temperature of the reaction vessel [0316 ] An emulsion polymer was prepared in the same contents was maintained at 65° C . for 60 minutes. The manner as Example 4 except that the monomer amount was reactor contents were then cooled to 60° C . A solution of changed to 30 wt. % (EA ) , 20 wt. % ( n -BA ) , 45 wt. % 1 . 96 grams of TBHP and 0 . 13 grams of 40 % AOS in 15 (HEMA ) and 5 wt. % (BEM ) instead of 35 wt. % (EA ) , 15 grams of DI water was added to the reactor. After 5 minutes , wt. % (n -BA ) , 45 wt. % (HEMA ) and 5 wt. % (BEM ). The a solution of 1 . 27 grams of erythorbic acid in 15 grams of polymer product had a solids content of 30 . 8 % , a viscosity DI water was added to the reactor. The reactor contents were of 26 cps and a particle size of 83 nm . maintained at 60° C . After 30 minutes, a solution of 1 . 96 grams of TBHP and 0 . 13 grams of 40 % AOS in 15 grams of Example 6 DI water was added to the reactor. After 5 minutes , a solution of 1 . 27 grams of erythorbic acid in 15 grams of DI Monomer Composition = EA / n -BA / HEMA / BEM water was added to the reactor . The reactor contents were ( 25 /25 /45 / 5 ) Wt. maintained at 60° C . for about 30 minutes . Then , the reactor contents were cooled to room temperature and filtered [0317 ] An emulsion polymer was prepared in the same through 100 micron filter cloth . The pH of the resulting manner as in Example 4 except that the monomer amount emulsion was adjusted to 4 . 5 with ammonium hydroxide . was changed to 25 wt. % (EA ), 25 wt. % (n -BA ), 45 wt. % The polymer product had a solids content of 30 .8 % , a (HEMA ) and 5 wt. % (BEM ) instead of 35 wt. % (EA ), 15 wt. % ( n -BA ) , 45 wt. % (HEMA ) and 5 wt. % (BEM ) . The viscosity of 24 cps and a particle size of 110 nm . polymer product had a solids content of 30 . 9 % , a viscosity Example 4 of 39 cps and a particle size of 78 nm . Monomer Composition = EA / n - BA /HEMA /BEM Example 7 ( 35 / 15 /45 / 5 ) Wt. Monomer Composition = EA / n -BA / HEMA/ BEM [0315 ] An emulsion polymer was prepared as follows. A (35 /20 /40 /5 ) Wt. monomer premix was made by mixing 140 grams of DI water, 5 grams of 100 % E - Sperse® RS - 1617 amphiphilic [ 0318 ] An emulsion polymer was prepared in the same crosslinker, 175 grams of (EA ), 75 grams of (n -BA ), 225 manner as Example 4 except that the monomer compositions gramsof (HEMA ) and 33 . 3 grams of (BEM ). Initiator Awas were changed to 35 wt. % (EA ), 20 wt. % ( n -BA ) , 40 wt. % made by dissolving 5 grams of Azo VA -086 in 40 grams of (HEMA ) and 5 wt. % (BEM ) instead of 35 wt. % (EA ) , 15 DI water. Initiator B was prepared by dissolving 2 . 5 grams wt. % (n - BA ) , 45 wt. % (HEMA ) and 5 wt. % (BEM ) . The of Azo VA - 086 in 100 grams of DI water . A 3 - liter reactor polymer product had a solids content of 31 . 4 % , a viscosity was charged with 800 grams of DI water, 5 grams of 40 % of 42 cps and a particle size of 87 nm . AOS and 10 grams of Selvol® 203 PVA . The contents of the reactor were heated to 87° C . under a nitrogen blanket with Example 8 agitation . After holding the reactor contents at 87° C . for one Monomer Composition = EA / n - BA / BEM /HEMA / AA hour, initiator A was added to the reactor. After about 1 minute , the monomer premix was metered to the reaction (35 /15 / 5 /43 /2 ) Wt. vessel over a period of 120 minutes . About 3 minutes after [ 0319 ] An emulsion polymer was prepared as follows. A the start of monomer premix introduction , initiator B was monomer premix was made by mixing 70 grams of DI water, metered to the reactor over a period of 150 minutes. The 2 .5 grams of E - Sperse® RS- 1618 amphiphilic crosslinker, reaction temperature was maintained at 87° C . After comple 87 . 5 grams of (EA ) , 37 . 5 grams of ( n -BA ) , 16 .67 grams of tion of the initiator B feed , the temperature of the reaction (BEM ), 107 . 5 grams of (HEMA ), and 5 grams of (AA ) . vessel contents were maintained at 87° C . for 60 minutes . Initiator No. 1 was made by dispersing 2 . 5 grams of VA -086 The reactor contents were then cooled to 49° C . A solution in 20 grams of DI water . Initiator No . 2 was prepared by of 0 .61 grams of TBHP and 0 .29 grams of 40 % AOS in 15 dissolving 1 .25 grams of VA -086 in 50 grams of DI water. grams of DI water was added to the reactor. After 5 minutes , A 1 - liter reactor vessel was charged with 400 grams of DI a solution of 0 .59 grams of erythorbic acid in 15 grams of water, 2 .5 grams of 40 % AOS and 5 grams of Selvol® 203 DI water was added to the reactor. The reactor contents were PVA and then the contents were heated to 87° C . under a maintained at 49° C . After 30 minutes, a solution of 0 .69 nitrogen blanket and agitation . Initiator No . 1 was added to grams of TBHP and 0 . 29 grams of 40 % AOS in 15 grams of the reaction vessel. The monomer premix was then metered DI water was added to the reactor. After 5 minutes, a into the reaction vessel over a period of 120 minutes ; while US 2017 /0367963 A1 Dec . 28 , 2017 34 at the same time, initiator No. 2 was metered to the reaction emulsion was adjusted to 3 .5 - 4 .5 with 28 % ammonium vessel over a period of 150 minutes . After the completion of hydroxide solution . The resulting polymer latex had a solid monomer premix feed , 16 . 5 grams of DI water was added to level of 30 . 4 % , and a particle size of 90 . 4 nm . the dropping funnel which held the monomer premix to flush out the residual monomers into the reaction mixture . After Example 10 the completion of initiator No . 2 feed , the temperature of the reaction vessel contents was maintained at 87° C . for 60 Monomer Composition = EA / n -BA /BEM /HEMA /MAMD minutes . The reaction vessel contents were then cooled to ( 35 / 15/ 5 /43 /2 ) Wt. 49° C . A solution of 0 . 3 grams of TBHP and 0 . 14 grams of [0321 ] An emulsion polymer was prepared as follows. A 40 % AOS in 7 . 5 grams of DIwater was added to the reaction monomer premix was made by mixing 70 grams of DI water, vessel. After 5 minutes , a solution of 0 . 3 grams of erythorbic 2 . 5 grams of E - Sperse® RS - 1618 amphiphilic crosslinker, acid in 7 . 5 grams of DI water was added to the reaction 87. 5 grams of ( EA ) , 37 . 5 grams of ( n -BA ) , 16 .67 grams of vessel . After 30 minutes , another solution of 0 . 3 grams of (BEM ) , 107 . 5 grams of (HEMA ) , and 20 grams 25 % TBHP and 0 . 14 grams of 40 % AOS in 7 . 5 grams of DI water (MAMD ) . Initiator No . 1 was made by dispersing 2 . 5 grams was added to the reaction vessel . A solution of 0 . 3 grams of of VA -086 in 20 grams of DI water . Initiator No. 2 was erythorbic acid in 7 . 5 grams of DI water was then added to prepared by dissolving 1. 25 grams of VA - 086 in 50 grams of the reaction vessel after 5 minutes . The reaction vessel DI water . A 1 - liter reactor vessel was charged with 400 contents were maintained at 60° C . for another 30 minutes. grams of DIwater , 2 .5 grams of 40 % AOS and 5 grams of The reaction vessel contents were then cooled to room Selvol® 203 PVA , and then the contents heated to 87° C . temperature ( 23° C . ) and filtered through a 100 micron filter under a nitrogen blanket and agitation . Initiator No . 1 was cloth . The pH of the resulting emulsion was adjusted to 3 . 5 added to the reaction vessel. The monomer premix was then to 4 . 5 with 28 % ammonium hydroxide in DI water. The metered to the reaction vessel over a period of 120 minutes ; resulting polymer latex had a solids level of 30 . 7 % , and a while at the same time, initiator No . 2 was metered to the particle size of 113 nm . reaction vessel over a period of 150 minutes. After the completion of monomer premix feed , 16 . 5 grams of DI Example 9 water was added to the dropping funnel which held the monomer premix to flush out the residual monomers . After Monomer Composition = EA /n -BA /BEM /HEMA / AMD the completion of initiator No . 2 feed , the temperature of the (35 / 15 /5 /43 /2 ) Wt. reaction vessel was maintained at 87° C . for 60 minutes. The [ 0320 ] An emulsion polymer was prepared as follows . A reaction vessel was then cooled to 49° C . A solution of 0 . 3 monomer premix was made by mixing 70 gramsof DIwater , grams of TBHP and 0 . 14 grams of 40 % AOS in 7 .5 grams 2 .5 grams of E - Sperse® RS - 1618 amphiphilic crosslinker, of DI water was added to the reaction vessel. After 5 87. 5 grams of (EA ) , 37 . 5 gramsof ( n - BA ), 16 .67 grams of minutes , a solution of 0 . 3 grams of erythorbic acid in 7 . 5 (BEM ), 107 .5 grams of 2 -hydroxyl ethyl methacrylate grams of DI water was added to the reaction vessel. After 30 (HEMA ) , and 10 grams 50 % acrylamide (AMD ) . Initiator minutes , another solution of 0 . 3 grams of TBHP and 0 . 14 No . 1 was made by dispersing 2 . 5 grams of VA -086 in 20 grams of 40 % AOS in 7 . 5 grams of DI water was added to grams of DI water . Initiator No. 2 was prepared by dissolv the reaction vessel. A solution of 0 . 3 grams of erythorbic ing 1 . 25 grams of VA - 086 in 50 grams of DI water. A 1 - liter acid in 7 . 5 grams of DI water was added to the reaction reactor vessel was charged with 400 grams of DI water, 2 . 5 vessel after 5 minutes . The reaction vessel contents were grams of 40 % AOS and 5 grams of Selvol® 203 PVA . The maintained at 60° C . for another 30 minutes . The reaction contents of the vessel was heated to 87° C . under a nitrogen vessel contents were cooled to room temperature and filtered blanket and agitation . Initiator No . 1 was added to the through a 100 micron filter cloth . The pH of the resulting reaction vessel. The monomer premix was then metered to emulsion was adjusted to 3 . 5 - 4 . 5 with a 28 % ammonium the reaction vessel over a period of 120 minutes , while at the hydroxide solution . The resulting polymer latex had a solid same time, initiator No . 2 was metered to the reaction vessel level of 26 . 2 % , and a particle size of 100 nm . over a period of 150 minutes. After the completion of monomer premix feed , 16 . 5 grams of DI water was added to Example 11 the dropping funnel which held the monomer premix to flush out the residualmonomers . After the completion of initiator Monomer Composition = EA / n -BA / BEM /HEMA / BEM No . 2 feed , the temperature of the reaction vessel contents ( 20 . 5 / 27 .5 / 45 / 7 ) Wt. wasmaintained at 87° C . for 60 minutes. The reaction vessel [0322 ] An emulsion polymer was prepared as follows. A contents were then cooled to 49° C . A solution of 0 . 3 grams monomer premix was made by mixing 140 grams of DI of TBHP and 0 . 14 grams of 40 % AOS in 7 . 5 grams of DI water, 5 grams of E -Sperse® RS - 1618 amphiphilic cross water was added to the reaction vessel . After 5 minutes, a linker, 102 . 5 grams of (EA ), 137. 5 grams of ( n -BA ) , 175 solution of 0 . 3 grams of erythorbic acid in 7 .5 grams of DI grams of (HEMA ), 46 .67 grams of (BEM ) . Initiator A was water was added to the reaction vessel. After 30 minutes , made by dissolving 5 grams of Azo VA -086 in 40 grams of another solution of 0 . 3 grams of TBHP and 0 . 14 grams of DI water. Initiator B was prepared by dissolving 2 . 5 grams 40 % AOS in 7 . 5 gramsof DI water was added to the reaction of Azo VA - 086 in 100 grams of DI water. A 3 - liter reactor vessel . A solution of 0 .3 grams of erythorbic acid in 7 .5 was charged with 800 grams of DI water , 5 grams of 40 % grams of DI water was then added to the reaction vessel after sodium alpha olefin sulfonate (AOS ) and 10 grams of 5 minutes . The reaction vessel contents were maintained at Selvol® 203 PVA , and then the contents were heated to 87° 60° C . for another 30 minutes . Then , the reaction vessel C . under a nitrogen blanket with agitation . After holding the contents were cooled to room temperature and filtered reactor contents at 87° C . for one hour, initiator A was then through a 100 micron filter cloth . The pH of the resulting added to the reactor. After about 2 to 3 minutes , the US 2017 /0367963 A1 Dec . 28 , 2017 35 monomer premix was metered into the reaction vessel over Example 13 a period of 120 minutes . About 1 minute after the start of monomer premix metering , Initiator B was metered into the Monomer Composition = EA /n -BA /HEMA / n - VP /CSEM reactor over a period of 150 minutes . The reaction tempera ( 23 / 20 / 35 / 20 / 2 ) Wt. ture was kept at 87° C . After completion of initiator B feed , the temperature of the reaction vessel contents were main [0324 ] An emulsion polymer was prepared as follows. A monomer premix was made by mixing 140 grams of DI tained at 87° C . for 60 minutes . The reactor contents were water, 5 grams of E -Sperse® RS - 1618 amphiphilic cross then cooled to 49° C . A solution of 0 . 61 grams of TBHP and linker, 115 grams of (EA ) , 100 grams of ( n -BA ) , 175 grams 0 .29 grams of 40 % AOS in 15 grams of DIwater was added of (HEMA ) , 12 . 5 grams (CSEM ) , and 100 grams of ( n - VP ) . to the reactor . After 5 minutes, a solution of 0 . 59 grams of Initiator A was made by dissolving 4 grams Azo VA -086 in erythorbic acid in 15 grams of DI water was added to the 40 grams of DI water. Initiator B was prepared by dissolving reactor. The reactor contents were maintained at 49° C . After 0 .75 grams of Azo VA - 086 in 100 grams of DI water. A 30 minutes, a solution of 0 .69 grams of TBHP and 0 . 29 3 - liter reactor was charged with 800 grams of DI water, 5 grams of 40 % AOS in 15 grams of DI water was added to grams of 40 % AOS and 20 grams of Selvol® 203 PVA , and the reactor. After 5 minutes, a solution of 0 .59 grams of then the contents were heated to 87° C . under a nitrogen erythorbic acid in 15 grams of DI water was added to the blanket with mild agitation . After holding the reactor con reactor. The reactor contents were maintained at 49° C . for tents at 87° C . for one hour Initiator A was then added to the about 30 minutes . The contents of the reactor were cooled to reactor . After about 1 minute , the monomer premix was room temperature and filtered through 100 micron filter metered into the reaction vessel for over a period of 120 cloth . The pH of the resulting emulsion was adjusted to 4 to minutes . About 3 minutes after the start ofmonomer premix 5 with a 28 % ammonium hydroxide solution . The polymer introduction , Initiator B was metered into the reactor over a was diluted with 340 grams of DI water to attain a solids period of 150 minutes. The reaction temperature was main 25 . 1 % , a viscosity 13 cps, and particle size 82 nm . tained at 87° C . After completion of the Initiator B feed , the temperature of the reaction vessel contents were maintained at 87° C . for an additional 60 minutes. The reactor contents Example 12 were then cooled to 49° C . A solution of 0 .61 grams of TBHP and 0 . 29 grams of 40 % AOS in 15 grams of DI water Monomer Composition = n - VP /EA /BA / Ac /HEMA was added to the reactor. After 5 minutes, a solution of 0 .59 ( 20/ 15/ 20/ 20/ 25) Wt. grams of erythorbic acid in 15 grams of DI water was added to the reactor. The reactor contents were maintained at 49° [ 0323] An emulsion polymer was prepared as follows . À C . After 30 minutes, a solution of 0 .69 grams of TBHP and monomer premix was made by mixing 70 grams of DI water, 0 .29 grams of 40 % AOS in 15 grams of DI water was added 2 .5 grams of E -Sperse® RS - 1618 amphiphilic crosslinker, to the reactor . After 5 minutes, a solution of 0 . 59 grams of 50 grams of ( n - VP ), 37. 5 grams of (EA ), 50 grams of erythorbic acid in 15 grams of DI water was added to the ( n - BA ), 50 grams of vinyl acetate ( VAc) , and 62 .5 grams of reactor. The reactor contents were maintained at 49° C . for (HEMA ). Initiator 1 was made by mixing 1 . 07 grams of about 30 minutes. The reactor contents were then cooled to TBHP in 20 gramsof DI water . Reductant 2 was prepared by the room temperature ( 23° C .) and filtered through 100 dissolving 0 .83 grams of erythorbic acid in 50 grams of DI micron filter cloth . The pH of the resulting emulsion was water. A 1 liter reactor vessel was charged with 400 grams adjusted to 4 . 5 with 10 % ammonium hydroxide in water. of DI water , 2 . 5 grams of 40 % AOS and 12 . 5 grams of The polymer emulsion had a solids content of 30 . 9 % , a Selvol® 502 PVA , and then the contents were heated to 65° Brookfield viscosity of 36 cps, and particle size 113 nm . C . under a nitrogen blanket and agitation . Initiator 1 was added to the reaction vessel. After about 1 minute , the Example 14 monomer premix was metered into the reaction vessel over F0325 ]. An antidandruff shampoo formulation is formu a period of 120 minutes ; while at the same time Reductant lated with the components set forth in the Table below . 2 was metered to the reaction vessel for over a period of 150 minutes. After the completion of monomer premix feed , TABLE 5 16 . 5 grams of DI water was added to flush the residual monomers from the premix vessel into the reaction vessel. Total Active Active Total Weight After the completion ofReductant 2 feed , the temperature of Ingredient ( wt. % ) ( wt. % ) ( g ) the reaction vessel contents were maintained at 65° C . for 60 Phase 1 minutes. The reaction vessel contents were then cooled to 50° C . A solution of 0 . 3 grams of TBHP and 7 . 5 grams of DI SLEL - 2 — Sodium 27 . 3 1212 . 0 219 . 78 Laureth Sulfate ( 2 water was added to the reaction vessel. After 5 minutes , a moles ethoxylation ) solution of 0 . 29 grams of erythorbic acid in 7 . 5 grams of DI SLS - Sodium Lauryl 29 . 00 2 .00 34 .48 water was added to the reaction vessel. After 30 minutes , a Sulfate solution of 0 . 32 grams of TBHP and 7 . 5 grams of DI water Cocamide MEA 100 .00 0 . 50 2 .50 was added to the reaction vessel. After 5 minutes , a solution Phase 2 of 0 .29 grams of erythorbic acid in 7 . 5 grams of DI water Deionized Water 75 . 00 was added to the reaction vessel . The reaction vessel con Polymer 30 . 57 2 .00 32 . 71 tents were maintained at 50° C . for about 30 minutes . Then , Phase 3 the reaction vessel was cooled to room temperature ( 22° C . ) Kathon ® Preservative 100 . 00 0 .05 0 . 25 and filtered through 100 micron filter cloth . The resulting Dow Corning® DC - 1491 60 . 00 2 .00 16 . 67 polymer latex had a solids level 30 . 8 % , and particle size 100 Silicone Microemulsionbeter o nm . US 2017 /0367963 A1 Dec . 28 , 2017 36

TABLE 5 - continued wherein said emulsion polymer is prepared from a polym erizable monomer composition comprising at least one Total Active Active Total Weight hydrophilic monomer and at least one hydrophobic mono Ingredient (wt . % (wt . % ) ( g ) mer , wherein said hydrophilic monomer is selected from Phase 4 hydroxy (C -C5 ) alkyl (meth )acrylates , N -vinyl amides, or mixtures thereof; wherein said hydrophobic monomer is D . I . Water 50 . 0 Jaguar ® C13 - S Guar 100 .00 0 . 20 1 .00 selected from esters of (meth )acrylic acid with alcohols Hydroxypropyltrimonium containing 1 to 30 carbon atoms, vinyl esters of aliphatic Chloride carboxylic acids containing 1 to 22 carbon atoms, vinyl Cocamidopropylbetaine 35 .00 0 . 15 2 .00 ethers of alcohols containing 1 to 22 carbon atoms, vinyl Phase 5 aromatic monomers, vinyl halides, vinylidene halides, asso Quickearl TM II Pearlizing 34 .00 2 .00 29 .41 ciative monomers , semi- hydrophobic monomers, or mix agent ( Sodium Laureth tures thereof , and at least one amphiphilic crosslinking agent Sulfate (and ) Glycol containing more than one unsaturated moiety Stearate ) Zinc Ormadine ® FPS 50 . 00 1 .00 10 .00 2 . A composition of claim 1 wherein said the at least one (zinc pyrithione) antidandruff agent is selected from a polyvalent metal salt of Phase 6 pyrithione . D . I . Water 20 . 0 3 . A composition of claim 2 wherein said the at least one Zinc Carbonate 97 . 00 1 .00 5 . 15 antidandruff agent is selected from at least one calcium , NaCl 100 .00 1 . 00 5 . 00 magnesium , barium , strontium , zinc , cadmium , tin , and MgSO4 100 . 00 18880 .50 2 . 50 zirconium metal salt of pyrithione . Phase 7 4 . A composition of claim 3 wherein said the at least one FD & C Blue # 1 2 Drops antidandruff agent is zinc pyrithione . NaOH 18. 0 aqueous q .s . to pH 7 . 8 5 . A composition of claim 4 further comprising a zinc (wt . /wt . ) containing layered material selected from basic zinc carbon ate , zinc carbonate hydroxide , hydrozincite , and combina [ 0326 ] Procedure: tions thereof. 1 . The Phase 1 ingredients are mixed as follows: SLES - 2 , SLS and Cocamide MEA are combined with gentle mixing 6 . A composition of claim 5 wherein said zinc layered and heated to 65 -70° C . until a homogenous solution is material is hydrozincite or basic zinc carbonate . obtained . 7 . A composition of claim 6 wherein said zinc layered 2 . The Phase 2 ingredients are mixed as follows: The material is basic zinc carbonate . nonionic , amphiphilic emulsion polymer is added to deion 8 . A composition of any of claim 2 wherein said the at ized water with gentle mixing . least one metal salt of pyrithione is present in an amount 3 . Once Phase 1 cools to 40° C . , Phase 1 is added to Phase ranging from about 0 .01 wt. % to about 5 wt. % in one aspect 2 under gentle mixing . and from about 0 .1 wt. % to about 2 wt. % in another aspect . 4 . The Phase 3 ingredients are combined with the Phase 9 . A composition of claim 5 wherein the weight ratio of 1 /Phase 2 mixture in the order listed in Table 5 under mixing . said zinc layered material to said the at least one metal salt 5 . In a separate vessel the ingredients of Phase 4 are of pyrithione is 5 : 100 to 10 :1 . combined and mixed until homogeneous and then added to 10 . A composition of claim 1 wherein said the at least one the combined Phase 1 / 2 / 3 mixture and mixed until fully antidandruff agent is selected from salicylic acid , elemental dispersed . sulfur, selenium dioxide , selenium sulfides , azole com 6 . The ingredients of Phase 5 are added to the combined pounds, hydroxy pyridone compounds, and combinations Phase 1 / 2 / 3 / 4 mixture in the order listed in Table 5 and thereof . mixed . 7 . Phase 6 is separately prepared by combining the ingre 11 . A composition of claim 10 wherein said the at least dients into a homogeneous mixture . The Phase 6 mixture is one antidandruff agent is present in an amount ranging from then added to the combined Phase 1 / 2 / 3 / 4 / 5 mixture and about 0 .01 wt. % . homogeneously mixed . 12 . A composition according to claim 1 wherein the 8 . FD & C Blue # 1 is added to the combined Phase 1 / 2 / 3 / 4 / amount of said emulsion polymer solids ranges from about 516 mixture and the pH is adjusted with 18 % sodium 0 . 5 to about 5 wt. % based on the weight of said composi hydroxide to 7 . 8 . tion . 9 . The final formulated shampoo product is allowed to 13 . A composition according to claim 1 wherein the equilibrate for 24 hours . amount of said surfactant ranges from about 5 wt. % to about [0327 ) The amount of silicon ( silicon atoms) deposited on 30 wt % ( active basis ) based on the weight of said compo hair tress samples treated with the shampoo composition can sition . be measured by X -Ray fluorescence (XRF ) spectroscopy in 14 . A composition according to claim 1 wherein the at accordance with the test methodology set forth above . least one surfactant is selected from an anionic surfactant 1. An antidandruff composition comprising in an aqueous and an amphoteric or zwitterionic surfactant. medium : 15 . A composition according to claim 14 wherein said a ) at least one surfactant selected from an anionic , ampho anionic surfactant is selected from sodium dodecyl sulfate , teric , and zwitterionic surfactant; ammonium dodecyl sulfate , sodium lauryl sulfate , sodium b ) at least one antidandruff agent; and trideceth sulfate , ammonium lauryl sulfate , sodium laureth c ) a nonionic , amphiphilic emulsion polymer; sulfate , ammonium laureth sulfate or mixtures thereof. US 2017 /0367963 A1 Dec . 28 , 2017 37

16 . A composition according to claim 14 wherein said wherein the alkylene moiety optionally can be substi amphoteric or zwitterionic surfactant is cocamidopropyl tuted by one or more methyl groups. betaine . 20 . A composition according to claim 1 wherein said 17 . A composition according to claim 1 wherein the N - vinyl amide is selected from a N - vinyllactam containing amphiphilic crosslinking agent is a compound of formula 4 to 9 atoms in the lactam ring moiety , wherein the ring ( III) : carbon atoms, optionally , can be substituted by one or more C1- Cz lower alkyl group . (III ) 21 . A composition according to claim 1 wherein said ester R - Motypnotre of (meth )acrylic acid with alcohols containing 1 to 30 carbon is selected from at least one compound represented by the formula :

(IV ) where : R10 R is a C10 - 24 alkyl, alkaryl, alkenyl, or cycloalkyl; R2 is CH3, CH2CH3, C6H5, or C14H29 ; Rz is H or Z M * Z is SOz , or PO , 2 ; wherein R9 is hydrogen or methyl and R1° is C , to C22 M * is Na +, K + , NH4 +, or an alkanolamine ; alkyl. x is 2 - 10 ; 22 . A composition according to claim 1 wherein said vinyl y is 0 - 200 ; and ester of aliphatic carboxylic acids containing 1 to 22 carbon z is 4 - 200 . atoms is selected from at least one compound represented by 18 . A composition according to claim 1 wherein the the formula : amphiphilic crosslinking agent is a compound of formula (IV ) : ( IV ) yo R11 wherein Rll is a C , to C22 aliphatic group which can be an alkyl or alkenyl. 23. A composition according to claim 1 wherein said vinyl ether of alcohols containing 1 to 22 carbon atoms is selected on otra from at least one compound represented by the formula : (VI ) DR13 wherein R13 is a C , to C22 alkyl. 24 . A composition according to claim 1 wherein said where : associative monomer comprises ( i) an ethylenically unsatu n is 1 or 2 ; rated end group portion ; ( ii ) a polyoxyalkylene mid - section z is 4 to 40 in one aspect ; and portion , and ( iii ) a hydrophobic end group portion contain R4 is H , SO3- M or PO , M + , and M is selected from Na+ , ing 8 to 30 carbon atoms. K + , NH + or an alkanolamine. 25 . A composition according to claim 24 wherein said 19 . A composition according to claim 1 wherein said associative monomer is represented by formulas VII and / or hydroxy (C7 -C5 ) alkyl (meth )acrylate is selected from at least VIIA : one compound represented by the formula :

VII R 14 RI- OH A + CH , , t07fR15 – 07, R16 D - A + CH27740 74R15 - 05 -R16 VIIA wherein R is hydrogen or methyl and Rl is an divalent alkylene moiety containing 1 to 5 carbon atoms, US 2017 /0367963 A1 Dec . 28 , 2017 38

wherein R14 is hydrogen ormethyl ; A is CH C ( O ) O - , C ( O ) O , 0 ~ , CHÚ0 , NHC ( O ) NH?, - continued C ( O ) NH , Ar ( CE ) ) - NHC ( 0 ) O < , = Ar D - A - CH277407m + R15 — 07 R17 ( CE ) - NHC( O ) NH , or CH?CH NHC( O ) = ; Ar is a divalent arylene ( e .g ., phenylene ); E is H or methyl; z is 0 or 1; k is an integer ranging from about 0 to about wherein R14 is hydrogen or methyl; A is CH C ( 0 ) 0 , 30 , and m is 0 or 1 , with the proviso that when k is 0 , m is 0 , and when k is in the range of 1 to about 30 , m COÀO , 02 , 2CH2O , NHC( O )NH? , is 1 ; D represents a vinyl or an allyl moiety ; (R15 _ O ) . C ( O )NH , Ar ( CE ) ) - NHCUOÀO , < Ar is a polyoxyalkylene moiety , which can be a homopo ( CE , ) - NHC( O ) NH , or – CHACH - NHC( 0 ) Ar is lymer, a random copolymer , or a block copolymer of a divalent arylene ( e .g ., phenylene ); E is H or methyl; C2- C4 oxyalkylene units , Ris is a divalent alkylene zis 0 or 1 ; k is an integer ranging from about 0 to about moiety selected from C2H4, C3H6, or C _Hg , and com 30 , and m is 0 or 1 , with the proviso that when k is 0 , binations thereof; and n is an integer in the range of m is 0 , and when k is in the range of 1 to about 30 , m about 2 to about 150 ; Y is — R150 , - RISNH — , is 1 ; (R15 _ O ), is a polyoxyalkylenemoiety , which can - C ( O ) - , - C ( O )NH — , R15NHC ( O )NH , or be a homopolymer, a random copolymer, or a block _ C ( O )NHC ( O ) ; R16 is a substituted or unsubsti copolymer of C , -C4 oxyalkylene units , R ' ) is a divalent tuted alkyl selected from a C8 -C30 linear alkyl, a C8- C30 alkylene moiety selected from C2H4, C3H6, or C4Hg, branched alkyl, a C2- C30 carbocyclic alkyl, a C2- C30 and combinations thereof; and n is an integer in the alkyl- substituted phenyl, an araalkyl substituted phe range of about 2 to about 150 ; R17 is selected from nyl, and an aryl- substituted C2- C30 alkyl; wherein the hydrogen and a linear or branched C - C4 alkyl group ; R alkyl group , aryl group , phenyl group optionally and D represents a vinyl or an allyl moiety . comprises one or more substituents selected from the 29 . A composition according to claim 1 wherein said group consisting of a hydroxyl group , an alkoxyl group , polymer is polymerized from a monomer mixture compris benzyl group styryl group , and a halogen group . ing at least 30 wt. % of said hydrophilic monomer ( s) and at 26 . A composition according to claim 24 wherein said least 5 wt. % of said hydrophobic monomers . associative monomer is represented by formula VIIB : 30 . A composition according to claim 1 wherein said amphiphilic polymer comprises a conventional crosslinking agent which is present in an amount sufficient to be incor VIIB porated into said polymer from about 0 .01 to about 1 wt. % , R based on the dry weight of the polymer . 20 - R15 - 07 - R16 31 . A composition according to claim 30 wherein the at least one conventional crosslinking agent is selected from polyallyl ethers of trimethylolpropane, polyallyl ethers of pentaerythritol, polyallyl ethers of sucrose , or mixtures thereof . wherein R14 is hydrogen or methyl; Ris is a divalent 32 . A composition according to claim 30 wherein the at alkylene moiety independently selected from C2H4, least one conventional crosslinking agent is selected from C2H6 , and C4Hg, and n represents an integer ranging pentaerythritol diallyl ether, pentaerythritol triallyl ether, from about 10 to about 60 , (R15 _ O ) can be arranged pentaerythritol tetraallyl ether; or mixtures thereof. in a random or a block configuration ; R16 is a substi 43 - 44 . ( canceled ) tuted or unsubstituted alkyl selected from a C8 -C30 33. A composition according to claim 1 wherein said linear alkyl, a Cg -C30 branched alkyl, a C8 -C30 carbo nonionic , amphiphilic emulsion polymer is prepared from a cyclic alkyl, a C2 - C30 alkyl- substituted phenyl, an monomer composition comprising : araalkyl substituted phenyl, and an aryl- substituted a ) from about 20 to about 60 wt. % of at least one C - C4 C2- C30 alkyl, wherein the Rºalkyl group , aryl group , hydroxyalkyl (meth ) acrylate ; phenyl group optionally comprises one or more sub b ) from about 10 to about 70 wt. % of at least one C , -C12 stituents selected from the group consisting of a alkyl (methacrylate ; hydroxyl group , an alkoxyl group , benzyl group styryl c ) from about 0 to about 40 wt. % of at least one vinyl group , and a halogen group . ester of a C - C10 carboxylic acid ; 27 . A composition according to claim 1 wherein said d ) from about 0 to about 30 wt. % of a vinyl lactam ; semi- hydrophobic monomer comprises ( i ) an ethylenically e ) from about to about 15 wt . % of at least one unsaturated end group portion ; ( ii ) a polyoxyalkylene mid associative and / or a semi- hydrophobic monomer section portion , and ( iii ) an end group portion selected from (wherein all monomer weight percentages are based on hydrogen or an alkyl group containing 1 to 4 carbon atoms . the weight of the total monomers ) ; and 28 . A composition according to claim 27 wherein said f ) from about 0 .01 to about 5 wt. % of at least one semi- hydrophobic monomer is selected from at least one crosslinker (based on the dry weight of the polymer ) monomer represented by formulas VIII and IX : selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and VIII said conventional crosslinking agent . R 14 34 . A composition according to claim 1 wherein said nonionic , amphiphilic emulsion polymer is prepared from a monomer composition comprising: 7 AFCH27, 407, + R13 – 0 + , - R17 a ) from about 20 to about 60 wt. % of at least one C , - C4 hydroxyalkyl (meth ) acrylate ; US 2017 /0367963 A1 Dec . 28 , 2017 39

b ) from about 10 to about 30 wt. % ethyl acrylate ; d ) from about 1 to about 10 wt. % of at least one c ) from about 10 to about 35 wt. % butyl acrylate ; associative and / or semi- hydrophobic monomer d ) from about 0 to about 25 wt. % of a vinyl ester of a (wherein all monomer weight percentages are based on carboxylic acid selected from vinyl formate , vinyl the weight of the total monomers ); and acetate , vinyl propionate, vinyl butyrate , vinyl isobu e ) from about 0 .01 to about 5 wt . % of at least one tyrate , and vinyl valerate ; crosslinker (based on the dry weight of the polymer ) e ) from about 0 to about 30 wt. % of vinyl pyrrolidone ; selected from an amphiphilic crosslinking agent or a f ) from about 0 to about 15 wt. % of at least one combination of an amphiphilic crosslinking agent and associative monomer and /or semi- hydrophobic mono said conventional crosslinking agent. mer (wherein all monomer weight percentages are 38 . A composition according to claim 1 wherein said based on the weight of the total monomers ) ; and nonionic , amphiphilic emulsion polymer is prepared from a g ) from about 0 .01 to about 5 wt. % of at least one monomer composition comprising : crosslinker ( based on the dry weight of the polymer ) a ) from about 20 to about 35 wt. % of hydroxyethyl selected from an amphiphilic crosslinking agent or a methacrylate ; combination of an amphiphilic crosslinking agent and b ) from about 10 to about 30 wt. % ethyl acrylate ; said conventional crosslinking agent. c ) from about 10 to about 30 wt. % butyl acrylate ; 35 . A composition according to claim 1 wherein said d ) from about 15 to about 25 wt. % of vinyl pyrrolidone , nonionic, amphiphilic emulsion polymer is prepared from a e ) from about 15 to about 25 wt. % of vinyl acetate monomer composition comprising : (wherein all monomer weight percentages are based on a ) from about 20 to about 50 wt. % of hydroxyethyl the weight of the total monomers ) ; and methacrylate ; f ) from about 0 .01 to about 5 wt. % of at least one b ) from about 10 to about 30 wt. % ethyl acrylate ; crosslinker (based on the dry weight of the polymer ) c ) from about 10 to about 30 wt. % butyl acrylate ; selected from an amphiphilic crosslinking agent or a d ) from about 0 to about 25 wt. % of vinyl pyrrolidone ; combination of an amphiphilic crosslinking agent and e ) from about 0 to about 25 wt. % of vinyl acetate ; said conventional crosslinking agent. f ) from about 0 to about 10 wt. % of at least one 39 . A composition according to claim 1 wherein said associative and /or semi- hydrophobic monomer nonionic , amphiphilic emulsion polymer is prepared from a (wherein all monomer weight percentages are based on monomer composition comprising: the weight of the total monomers ); and a ) from about 20 to about 40 wt. % of hydroxyethyl g ) from about 0 .01 to about 5 wt. % of at least one methacrylate ; crosslinker ( based on the dry weight of the polymer ) b ) from about 10 to about 30 wt. % ethyl acrylate ; selected from an amphiphilic crosslinking agent or a c ) from about 10 to about 30 wt. % butyl acrylate ; combination of an amphiphilic crosslinking agent and d ) from about 15 to about 25 wt. % of vinyl pyrrolidone; said conventional crosslinking agent . e ) from about 1 to about 5 wt % of at least one associative 36 . A composition according to claim 1 wherein said and / or semi- hydrophobic monomer (wherein all mono nonionic , amphiphilic emulsion polymer is prepared from a mer weight percentages are based on the weight of the monomer composition comprising : total monomers ) ; and a ) from about 20 to about 50 wt. % of hydroxyethyl e ) from about 0 .01 to about 5 wt. % of at least one methacrylate ; crosslinker (based on the dry weight of the polymer ) b ) from about 10 to about 40 wt. % ethyl acrylate ; selected from an amphiphilic crosslinking agent or a c ) from about 10 to about 20 wt. % butyl acrylate ; combination of an amphiphilic crosslinking agent and d ) from about 0 . 1 to about 10 wt. % of at least one said conventional crosslinking agent. associative and / or semi-hydrophobic monomer 52 -53 . (canceled ) (wherein all monomer weight percentages are based on 40 . A composition according to claim 1 wherein said the weight of the total monomers ); and composition further comprises a conditioning agent selected e ) from about 0 .01 to about 5 wt. % of at least one from a cationic compound , a cationic polymer, an ampho crosslinker ( based on the dry weight of the polymer ) lytic polymer, a silicone , a hydrocarbon oil , a natural oil, a selected from an amphiphilic crosslinking agent or a natural wax , a synthetic wax , and combinations thereof . combination of an amphiphilic crosslinking agent and 41 . A composition according to claim 1 wherein said said conventional crosslinking agent. composition is selected from shampoos, baby shampoos , 37 . A composition according to claim 1 wherein said body washes , shower gels , liquid hand soaps , pet cleansing nonionic, amphiphilic emulsion polymer is prepared from a product, or facial cleansers . monomer composition comprising : 42. A method for enhancing the phase stability of an a ) from about 20 to about 50 wt. % of hydroxyethyl antidandruff shampoo composition comprising adding methacrylate ; thereto a nonionic , amphiphilic emulsion , emulsion polymer b ) from about 10 to about 30 wt. % ethyl acrylate; as set forth in claim 1 . c ) from about 10 to about 30 wt. % butyl acrylate ; * * * * *